KR102483732B1 - A process for the preparation of a graft copolymer comprising a polyolefin main chain and one or a multiple polymer side chains and the products obtained therefrom - Google Patents

Abstract

The present invention relates to a cascade process for the preparation of graft copolymers comprising a polyolefin backbone and one or more polymer side chains. The method comprises A) i) a metal catalyst or metal catalyst precursor comprising a metal from Groups 3-10 of the IUPAC Periodic Table of Elements; and ii) copolymerizing at least one metal-pacified functional olefin monomer with at least one first type olefin monomer and at least one second type olefin monomer using a catalyst system, optionally comprising a co-catalyst. Obtaining a polyolefin main chain having functional short chain branches coordinated with a metal of and B) forming one or more polymeric side chains on the polyolefin main chain having functional short chain branches coordinated with one or more metals to obtain a graft copolymer.

Description

Method for preparing a graft copolymer comprising a polyolefin main chain and one or more polymer side chains and products obtained therefrom OBTAINED THEREFROM}

The present invention relates to a process for preparing a graft copolymer comprising a polyolefin main chain and one or more polymer side chains using a cascade-like process and products obtained therefrom.

The present invention relates to a process for preparing a copolymer having a polyolefin backbone containing one or more polar or non-polar side chains and products obtained therefrom.

Graft copolymers having a polyolefin backbone attached to at least one non-polar polyethylene-like polymer side chain are useful, for example, as compatibilizers for polyolefins (eg, iPP) and polyethylene blends. In fact, the preparation of polyolefin-polyethylene graft copolymers (eg iPP-g-PE) is a very tedious process.

Graft copolymers, in which the polyolefin backbone is attached to at least one type of polar polymer side chain, present problems in certain applications because of their inherent non-polar nature, poor adhesion, printability, and compatibility that can limit efficacy. It can be used to improve the properties of polyolefin polymers. In addition, these graft copolymers are useful as compatibilizers for, for example, polyolefin (eg iPP) and polar polymer (eg polycarbonate) blends.

It is known that graft copolymers can be prepared using as the backbone a well-defined, randomly functionalized polyolefin containing functional short-chain branches. These main chain polyolefins are produced in a separate process in which side chains are added using an additional catalyst in a subsequent process.

In another related prior art (Becquart, Macromol. Mater. Eng. 2009, 294, 643-650) poly(ethylene-co-vinyl alcohol) (EVOH) is applied as a poly(hydroxyl) functional polyethylene, transesterification A process was used in which polyester was treated in the presence of SnOct ₂ as a catalyst to form the corresponding EVOH-graft-polyester graft copolymer.

Formation of polar or non-polar polymer side chains can be achieved by either growing these polymer side chains from reactive substituents on the polyolefin backbone (grafting from the access object) or by attaching pre-synthesized polymers to the reactive side chains of the polyolefin backbone (grafting onto the access object). ) can be performed.

An object of the present invention is to provide an easy, universal and controllable process for the preparation of graft copolymers.

It is also an object of the present invention to prepare a graft copolymer having a polyolefin backbone and at least one kind of polar or non-polar polymer (preferably polyethylene-like polyester) polymer side chain.

Another object of the present invention is to provide copolymers that can be used as compatibilizers of blends of polyolefins and polar polymers, such as iPP and polycarbonate, or blends of polyolefins and non-polar polymers, such as iPP and PE.

One or more of these objects is achieved by the method according to the present invention.

Summary of Invention

The present invention relates to a novel and ingenious cascade-type process for the preparation of graft copolymers comprising a polyolefin backbone and one or more polymer side chains and products obtained therefrom.

In a first aspect, the present invention relates to a process for preparing a graft copolymer comprising a polyolefin backbone and one or more polymer side chains, comprising the steps of:

A) i) a metal catalyst or metal catalyst precursor comprising a metal of groups 3-10 of the IUPAC Periodic Table of Elements; and

ii) optionally a co-catalyst;

One or more metal-pacified functional olefin monomers are copolymerized with at least one first type olefin monomer and at least one second type metal-pacified functional olefin monomer using a catalyst system comprising Obtaining a polyolefin main chain having short chain branches;

B) forming one or more polymeric side chains on the polyolefin backbone, wherein the metal-adjusted functional short-chain branch on the polyolefin backbone obtained in step A) is used as a catalytic initiator to obtain a graft copolymer.

In one embodiment, the catalyst system further comprises iii) optionally a scavenger.

Step B) can be carried out, for example, by ring opening polymerization (ROP) and/or nucleophilic substitution.

In one embodiment, step B) to obtain the graft copolymer may be carried out by ring-opening polymerization (ROP) using at least one kind of cyclic monomer.

In one embodiment, step B) for obtaining the graft copolymer comprises a nucleophilic substitution reaction, in particular for example an ester, at a carbonyl group-containing functional group, in particular for example a carboxylic acid or carbonic acid ester function, of at least one polymer for the side chain. It can be carried out by an exchange reaction.

In one embodiment, the first type of olefin monomer is a compound according to Formula I-A:

[Formula I-A]

In the above formula,

C is carbon;

R ^1a , R ^1b , R ^1c , and R ^1d are each independently selected from the group consisting of H or hydrocarbyl of 1 to 16 carbon atoms; or,
The first type of olefin monomer is selected from the group consisting of 1-cyclopentene, cyclohexene, norbornene, ethylidene-norbornene, vinylidene-norbornene, and combinations of one or more thereof.

In another embodiment, the functional olefin monomer tuned with the second type of metal is a compound according to Formula I-B:

[Formula I-B]

In the above formula,

C is carbon;

R ² , R ³ , and R ⁴ are each independently selected from the group consisting of H or hydrocarbyl of 1 to 16 carbon atoms;

R ⁵ -X-ML _n is a heteroatom-containing functional group coordinated with a main group metal, wherein X is a heteroatom or heteroatom-containing group, and the heteroatom bonded to M is selected from the group consisting of O, S and N is; R ⁵ is hydrocarbylene having 1 to 16 carbon atoms.

In another embodiment, step B) is carried out immediately after step A), preferably continuously, preferably in a series of connected reactors.

In another embodiment, no additional catalyst is added besides the catalytic initiator for the ROP or nucleophilic substitution reaction during step B).

In another embodiment, the metal catalyst or metal catalyst precursor used in step A) comprises a metal from Groups 3-8, preferably 3-6, more preferably 3-4 of the IUPAC Periodic Table of Elements.

In another embodiment, the metal catalyst or metal catalyst precursor used in step A) is selected from the group consisting of Ti, Zr, Hf, V, Cr, Fe, Co, Ni, Pd, preferably Ti, Zr or Hf contains metal

In one embodiment, the catalyst is a Ziegler-Natta catalyst, for example a titanium-magnesium and aluminum based Ziegler-Natta catalyst obtainable by reacting in particular a titanium alkoxy with a magnesium alkoxy and then reacting the reaction product with an aluminum alkyl halide. , or in particular catalysts based on Group 4 metals, which may be, for example, metallocenes, half-metallocenes or post-metallocenes and/or single site catalysts.

In one embodiment, the catalyst precursor is, for example, a C _s -, C ₁ - or C ₂ -symmetric zirconium or hafnium metallocene, preferably an indenyl substituted zirconium or hafnium dihalide, more preferably a crosslinked bis-indenyl zirconium or hafnium dihalide, even more preferably rac -dimethylsilyl bis-indenyl zirconium or hafnium dichloride ( rac -Me ₂ Si(Ind) ₂ ZrCl ₂ and rac -Me ₂ Si(Ind) respectively) ₂ HfCl ₂ ), or rac -dimethylsilyl bis-(2-methyl-4-phenyl-indenyl) zirconium or hafnium dichloride ( rac -Me ₂ Si(2-Me-4-Ph-Ind) ₂ ZrCl ₂ respectively and rac -Me ₂ Si(2-Me-4-Ph-Ind) ₂ HfCl ₂ ).

In one embodiment, the catalyst precursor is, for example, a so-called half-metallocene, or constrained structure catalyst, even more preferably, C ₅ Me ₅ [(C ₆ H ₁₁ ) ₃ P=N]TiCl ₂ , [Me ₂ Si(C ₅ Me ₄ )N(tBu)]TiCl ₂ , [C ₅ Me ₄ (CH ₂ CH ₂ NMe ₂ ]TiCl ₂ ).

In one embodiment, the catalyst is, for example, a so-called post-metallocene, preferably [Et ₂ NC(N(2,6-iPr ₂ -C ₆ H ₃ )]TiCl ₃ or [N-(2 ,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium dimethyl.

In another embodiment, the co-catalyst is an aluminum alkyl and an aluminum alkyl halide such as triethyl aluminum (TEA) or diethyl aluminum chloride (DEAC), or MAO, DMAO, MMAO, SMAO and fluorinated aryl boranes or fluorinated aryl borates. is selected from the group consisting of

In another embodiment, the scavenger is an aluminum alkyl such as tri(i-butyl) aluminum, trioctyl aluminum, trimethyl aluminum, MAO, MMAO, SMAO, a zinc alkyl such as diethyl zinc, or a magnesium alkyl such as dibutyl magnesium. is selected from the group consisting of In one embodiment, the scavenger is the same compound as the co-catalyst. In another embodiment, the scavenger is a different compound than the co-catalyst. Scavengers can also act as chain transfer agents.

In another embodiment, the olefin monomer according to Formula I-A is ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1 -decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, and combinations of one or more thereof. is selected from the group consisting of

In another embodiment, the cyclic monomer used during the ROP in step B) is a lactone, lactide, cyclic oligoester (eg a di-ester, tri-ester, tetra-ester, penta-ester or higher oligoester) , epoxide, aziridine, combination of epoxide and/or aziridine and CO ₂ , cyclic anhydride, combination of epoxide and/or aziridine and cyclic anhydride, epoxide and/or aziridine and CO ₂ and a polar monomer selected from the group consisting of combinations of cyclic anhydrides, cyclic N-carboxyanhydrides, cyclic carbonates, lactams, and combinations of one or more thereof.

In another embodiment, the cyclic monomer used during ROP in step B) is a cyclic monomer having a carbonyl group-containing functional group and at least 12 or at least 10 consecutive carbon atoms in the ring/cycle, preferably between click esters such as macrolactones, cyclic carbonates, cyclic amides, cyclic urethanes and cyclic ureas; or combinations of one or more thereof, preferably macrolactones.

In another embodiment, the polymer for the side chain comprising at least a carboxylic acid or carbonic ester functional group, or a carbonyl group-containing functional group, is a polyester, polycarbonate, polyamide, polyurethane, polyurea, random or block poly(carbonate-ester ), poly(carbonate-ether), poly(ester-ether), poly(carbonate-ether-ester), poly(ester-amide), poly(ester-ether-amide), poly(carbonate-amide), poly( carbonate-ether-amide), poly(ester-urethane), poly(ester-ether-urethane), poly(carbonate-urethane), poly(carbonate-ether-urethane), poly(ester-urea), poly(ester-urethane) ether-urea), poly(carbonate-urea), poly(carbonate-ether-urea), poly(ether-amide), poly(amide-urethane), poly(amide-urea), poly(urethane-urea) or one It is selected from the group consisting of combinations of the above.

In another embodiment, the coordinating metal used to obtain the metal-tuned functional olefin monomer is selected from the group consisting of magnesium, calcium, boron, aluminum, gallium, bismuth, titanium, zinc, and combinations of one or more thereof. .

In one embodiment, the method of the present invention does not include the presence of a polymer-OH intermediate.

In another aspect of the invention, the invention relates to a graft copolymer obtained or obtainable by the process according to the invention.

Justice

The following definitions are used in this specification and claims. Other terms not mentioned below are intended to have the generally accepted meaning in the art.

As used herein, “graft copolymer” refers to a polymer having one or more side chains linked to a main chain. These side chains have different structural or constitutive characteristics from those of the main chain.

As used herein, “backbone chain” refers to a linear polymer chain from which all other chains can be considered pendant. The backbone is preferably also the starting polymer chain from which other chains/side chains can be obtained. The backbone is thus obtained in step A).

As used herein, "side chain" or "branch" or "polymer branch" or "polymer side chain" refers to a branch from a polymer backbone. These terms may be used interchangeably. This branch may be oligomeric or polymeric and may be similar or different in nature to the polymer backbone. A “side chain” or “branch” or “polymer branch” or “polymer side chain” can thus also be a random or block copolymer comprising at least two different monomers. "Side chains" can be obtained starting from the main chain. Thus "side chains" can be obtained in step B).

"Short chain branching" as used herein means a branch having only a small number of atoms. Short chain branches are much smaller than the backbone of the linear molecule to which they are attached.

As used herein, "side group" refers to a branch from a chain that is neither an oligomer nor a polymer.

As used herein, “olefin monomer” or “olefin” refers to a hydrocarbon compound having a carbon-carbon double bond that can function as a building block of a polyolefin.

As used herein, "α-olefin" means an olefin having a double bond at the α position.

As used herein, “polyolefin” means a polymer obtained by polymerization of olefin monomers.

As used herein, “polymer chain” means a chain having a number average molecular weight ( M _n ) of at least 500 g/mol.

As used herein, "copolymer" means a polymer derived from more than one monomer.

As used herein, “copolymerization” refers to a process for producing copolymers in which at least two different monomers are used.

As used herein, “pacifying agent” means an agent that blocks or protects a functional group such that the functional group is reversibly inactivated.

As used herein, "metal-pacified functional olefin monomer" means an olefin monomer having a reactive functional group that reacts with a metal. It is a functional olefin monomer tuned using a metal for reversible inactivation of the functional group.

As used herein, “functional short-chain branching coordinated with a metal” refers to a short-chain branching having a reactive functional group that reacts with a metal. It is a functional short-chain branch that is coordinated using metals for reversible inactivation of the functional group.

"Hydrocarbyl chain" as used herein refers to the hydrocarbyl product of the polymerization reaction according to step A) of the present invention. It can be an oligomeric polyolefin chain having, for example, 2 to 20 olefin units, or it can be a polyolefin chain composed of more than 20 olefin units. It should be noted that "hydrocarbyl chain" and "hydrocarbyl" are not used synonymously.

As used herein, “hydrocarbyl” refers to a substituent containing hydrogen and carbon atoms; These include linear, branched or cyclic saturated or unsaturated aliphatic substituents such as alkyl, alkenyl, alkadienyl and alkynyl; alicyclic substituents such as cycloalkyl, cycloalkadienyl, cycloalkenyl; aromatic substituents, such as monocyclic or polycyclic aromatic substituents, as well as combinations thereof, such as alkyl-substituted aryls and aryl-substituted alkyls. They may be substituted with one or more non-hydrocarbyl, heteroatom-containing substituents. Thus, when "hydrocarbyl" is used herein, it may also be "substituted hydrocarbyl" unless otherwise specified. Perfluorinated hydrocarbyls in which all hydrogen atoms are replaced by fluorine atoms are also included in the term "hydrocarbyl". Hydrocarbyl can exist as a group on a compound (hydrocarbyl group) or as a ligand on a metal (hydrocarbyl ligand).

As used herein, "polyethylene-like block" or "polyethylene-like polymer" or "polyethylene-like polymer block" is a polymer or polymer block that is at least partially miscible with polyethylene, including but not limited to, for example, polyethylene-like polyester blocks. means A polymer or polymer block of this kind may contain at least 60 mol% of at least 10 consecutive monomeric units between carbonyl group-containing functional groups. Thus, in the context of the present invention, polyethylene-like polymers are considered to be non-polar.

As used herein, "cyclic monomer" refers to a compound having a ring system that can be used as a building block during polymerization. The ring system opens and the ring-opened monomer attaches to the growing polymer chain.

As used herein, “ring-opening polymerization” or “ROP” refers to a form of chain-growth polymerization in which cyclic monomers ring-open and join a chain to form a polymer. This also includes copolymerization of cyclic monomers with carbon dioxide (eg epoxy + C0 ₂ ).

As used herein, “initiator” refers to a reagent capable of initiating a ROP or nucleophilic substitution reaction when used in conjunction with a metal catalyst.

As used herein, "catalytic initiator" means a metal-containing reagent capable of initiating and catalyzing ROP or nucleophilic substitution reactions. In other words, a catalytic initiator is a combination of a metal catalyst and an initiator.

As used herein, “Lewis base ligand” refers to a group capable of coordinating to a transition metal of a metal catalyst or metal catalyst precursor.

"Pol" as used herein means polyolefin.

"PE" as used herein means polyethylene.

As used herein, "LDPE" means low density polyethylene.

As used herein, "LLDPE" means linear low density polyethylene. LDPE and LLDPE thus include polyethylene having a density of eg from 0.85 to 0.95 kg/m ³ , and may therefore also include in particular VLDPE and MDPE, for example.

"HDPE" as used herein means high density polyethylene.

As used herein, “CL” means ε-caprolactone.

"PCL" as used herein means polycaprolactone.

As used herein, "PLA" means polylactide (L, D or DL lactide may be used).

As used herein, "aPP" means atactic polypropylene.

As used herein, “iPP” refers to isotactic polypropylene.

As used herein, “sPP” refers to syndiotactic polypropylene.

As used herein, "EB" means cyclic ethylene brassylate.

As used herein, "PEB" means polyethylene brassylate.

As used herein, "Amb" refers to ambretolide.

As used herein, “PAmb” means polyambretolide.

"BA" as used herein means cyclic butylene adipate.

As used herein, "PBA" means polybutyl adipate.

As used herein, "BS" means cyclic butylene succinate.

As used herein, "PBS" means polybutylsuccinate.

As used herein, "aPS" means atactic polystyrene.

As used herein, "iPS" means isotactic polystyrene.

As used herein, "sPS" means syndiotactic polystyrene.

As used herein, "PDL" means pentadecalactone.

"PPDL" as used herein means polypentadecalactone.

As used herein, “4M1P” means 4-methyl-1-pentene.

As used herein, “P4M1P” means poly-4-methyl-1-pentene.

As used herein, “iP4M1P” refers to isotactic poly-4-methyl-1-pentene.

As used herein, "-g-" means a graft copolymer, and for example, HDPE-g-PCL is a graft copolymer of PCL grafted onto HDPE.

As used herein, “-co-” means a random copolymer, for example poly (CL-co-PDL) is a random copolymer of CL and PDL.

As used herein, "nucleophilic substitution" refers to a reaction in which a nucleophile attached to a carbonyl group is replaced by another nucleophile.

As used herein, “transesterification” refers to the process of exchanging nucleophilic alkoxy groups of carboxylic acid or carbonic acid esters. Transesterification is a special type of nucleophilic substitution with an ester or carbonate functional group.

As used herein, "carboxylic acid ester functional group" means an ester group (-O-C(=O)-) bonded to an organic hydrocarbyl group.

As used herein, "carbonate ester functional group" means a carbonate group (-O-C(=O)-O-) bonded to an organic hydrocarbyl group.

As used herein, "carbonyl group-containing functional group" means a carbonyl (>C=O) group bonded to an organic heteroatom-containing group XR', wherein X is selected from O, S and NR", wherein R' and R" are hydrogen or hydrocarbyl, and the carbonyl group is attached to the heteroatom. In the context of the present invention, preferably, the polymer for the side chain contains at least one carboxylic acid ester, carbonic acid ester, amide, urethane or urea functional group as the carbonyl group-containing functional group. The term carbonyl group-containing functional group also includes functional groups other than carboxylic acid and carbonic acid ester functional groups. Thus, a carbonyl group-containing functional group preferably refers to a reactive carbonyl group-containing functional group. Accordingly, it preferably does not mean a ketone in the context of the present invention.

As used herein, "cyclic ester" means an ester compound in a cyclic form. It also includes cyclic oligoesters which are cyclic di-esters, cyclic tri-esters, cyclic tetra-esters, cyclic penta-esters or higher cyclic oligomeric esters.

As used herein, “lactone” refers to a cyclic ester of a hydroxycarboxylic acid. This is included in the definition of cyclic esters.

As used herein, “oligolactone” refers to a di-lactone, tri-lactone, tetra-lactone, penta-lactone or higher oligomeric lactone. These are special types of lactones and are included in the definition of lactones.

As used herein, “macrolactone” means a macrocyclic lactone, wherein the lactone contains at least 10 contiguous carbon atoms and an ester functional group in the ring/cycle. These are special types of lactones and are included in the definition of lactones.

These are special types of lactones and are included in the definition of lactones.

As used herein, "macrooligolactone" refers to a mixture of cyclic macromono-, macrodi-, macrotri-, macrotetra- and macropenta-lactones or higher oligomers. These are special types of macrolactones and are included in the definition of macrolactones.

As used herein, “cyclic amide” refers to an amide compound in a cyclic form. It also includes cyclic oligoamides which are cyclic di-amides, cyclic tri-amides, cyclic tetra-amides, cyclic penta-amides or higher cyclic oligomeric amides.

As used herein, “cyclic carbonate” refers to a carbonate compound in a cyclic form. It also includes cyclic oligocarbonates which are cyclic di-carbonates, cyclic tri-carbonates, cyclic tetra-carbonates, cyclic penta-carbonates or higher cyclic oligomeric carbonates.

As used herein, "cyclic urethane" means a urethane compound in a cyclic form. It also includes cyclic oligourethanes which are cyclic di-urethanes, cyclic tri-urethanes, cyclic tetra-urethanes, cyclic penta-urethanes or higher cyclic oligomeric urethanes.

As used herein, "cyclic urea" refers to a urea compound in a cyclic form. It also includes cyclic oligoureas, which are cyclic di-ureas, cyclic tri-ureas, cyclic tetra-ureas, cyclic penta-ureas or higher order cyclic oligomeric ureas.

As used herein, “HT SEC” refers to high temperature size exclusion chromatography. HT SEC can be used as a measure of both size and polydispersity of a polymer.

As used herein, "polydispersity index ( Ð )" means a value representing the size distribution of polymer molecules ( M _w /M _n ). The measurement method of Ð will be described later. M _n is the number average molecular weight, and M _w is the weight average molecular weight.

As used herein, "chain transfer agent" means a compound capable of enabling the interchange of hydrocarbyl and/or hydrocarbyl chains with an active catalyst or other chain transfer agent. It is a metal compound comprising at least one ligand with weak chemical bonds.

As used herein, “catalyst system” means a system comprising a metal catalyst or metal catalyst precursor and optionally a co-catalyst and optionally a scavenger.

As used herein, “catalyst” refers to a species that provides a catalytic reaction.

As used herein, "metal catalyst" means a catalyst comprising at least one metal center forming an active site. In the context of the present invention, a "metal catalyst" is the same as a "transition metal catalyst" where the metal is a transition metal.

As used herein, “metal catalyst precursor” refers to a compound that upon activation forms an active metal catalyst.

As used herein, “metallocene” refers to a metal catalyst or metal catalyst precursor that typically consists of two substituted cyclopentadienyl (Cp) ligands bound to metal active sites.

As used herein, “transition metal” refers to any metal of Groups 3-10 of the IUPAC Periodic Table of Elements, or in other words, a Group 3 metal, a Group 4 metal, a Group 5 metal, a Group 6 metal, a Group 7 metal, a Group 8 metal, Group 9 metal or Group 10 metal.

As used herein, “group 3 metals” are metals selected from group 3 of the IUPAC periodic table of elements, namely scandium (Sc), yttrium (Y), lanthanum (La) and other lanthanides (Ce-Lu) and actinium (AC). and other actinides (Th-Lr).

"Group 4 metal" as used herein means a metal selected from Group 4 of the IUPAC Periodic Table of Elements, namely titanium (Ti), zirconium (Zr) and hafnium (Hf).

As used herein, "group 5 metal" means a metal selected from group 5 of the IUPAC Periodic Table of Elements, namely vanadium (V), niobium (Nb) and tantalum (Ta).

As used herein, "group 6 metal" means a metal selected from group 6 of the IUPAC Periodic Table of Elements, namely chromium (Cr), molybdenum (Mo) and tungsten (W).

As used herein, "group 7 metal" means a metal selected from group 7 of the IUPAC Periodic Table of Elements, namely manganese (Mn), technetium (Tc) and rhenium (Re).

As used herein, "group 8 metal" means a metal selected from group 8 of the IUPAC Periodic Table of Elements, namely iron (Fe), ruthenium (Ru) and osmium (Os).

As used herein, "group 9 metal" means a metal selected from group 9 of the IUPAC periodic table of elements, namely cobalt (Co), rhodium (Rh), and iridium (Ir).

As used herein, "group 10 metal" means a metal selected from group 10 of the IUPAC Periodic Table of Elements, namely nickel (Ni), palladium (Pd) and platinum (Pt).

As used herein, "main group metal" refers to a metal that is an element of Groups 1, 2, and 13-15 of the IUPAC Periodic Table of Elements. In other words, the following metals:

^* Group 1: lithium (Li), sodium (Na) and potassium (K)

^* Group 2: Beryllium (Be), Magnesium (Mg) and Calcium (Ca)

^* Group 13: boron (B), aluminum (Al), gallium (Ga) and indium (In)

^* Group 14: Germanium (Ge) and Tin (Sn)

^* Group 15: antimony (Sb) and bismuth (Bi).

Main group metals also include zinc (Zn) in the context of the present invention.

As used herein, "cocatalyst" means a compound that activates a metal catalyst precursor to obtain an active metal catalyst.

As used herein, “scavenger” means a compound that prevents poisoning of the catalyst by reacting with impurities present in the polymerization reactor, solvent, and monomer feed during the olefin polymerization process.

As used herein, "methylaluminoxane" or "MAO" means a compound derived from the partial hydrolysis of trimethyl aluminum which serves as a co-catalyst for catalytic olefin polymerization.

As used herein, “SMAO” refers to supported methylaluminoxane, ie, methylaluminoxane bound to a solid support.

As used herein, “DMAO” means devoid methylaluminoxane, i.e. methylaluminoxane from which free trimethyl aluminum has been removed.

As used herein, “MMAO” refers to modified methylaluminoxanes, i.e. products obtained after partial hydrolysis of trimethyl aluminum as well as other trialkyl aluminum such as tri(i-butyl) aluminum or tri-n-octyl aluminum. .

"Fluorinated aryl borane or fluorinated aryl borate" as used herein means a borate compound with tri- or tetrafluorinated (preferably perfluorinated) aryl ligands or a borane compound with trifluorinated (preferably perfluorinated) aryl ligands. do.

As used herein, "halide" refers to an ion selected from the group consisting of fluoride (F ^- ), chloride (Cl ^- ), bromide (Br ^- ) and iodide (I ^- ).

As used herein, “halogen” refers to an atom selected from the group consisting of fluorine (F), chlorine (Cl), bromine (Br) and iodine (I).

As used herein, "heteroatom" means an atom other than carbon or hydrogen. Heteroatoms include halides.

As used herein, "heteroatom selected from Groups 14, 15, 16 or 17 of the IUPAC Periodic Table of the Elements" means Si, Ge, Sn [Group 14], N, P, As, Sb, Bi [Group 15] , O, S, Se, Te [Group 16], F, Cl, Br, and I [Group 17].

As used herein, “alkyl” refers to a group composed of carbon and hydrogen atoms having only single carbon-carbon bonds. Alkyl groups may be substituted or unsubstituted, straight-chain or branched-chain. It may contain aryl substituents. It contains one or more heteroatoms such as oxygen (O), nitrogen (N), phosphorus (P), silicon (Si), tin (Sn) or sulfur (S) or halogen (i.e. F, CI, Br, I). It may or may not include.

As used herein, “aryl” refers to a substituent derived from an aromatic ring. An aryl group is one or more heteroatoms such as oxygen (O), nitrogen (N), phosphorus (P), silicon (Si), tin (Sn) or sulfur (S) or a halogen (i.e. F, CI, Br, I) may or may not include. Aryl groups also encompass substituted aryl groups in which one or more hydrogen atoms on the aromatic ring are replaced with a hydrocarbyl group.

“Alkoxide” or “alkoxy” as used herein refers to a substituent obtained by deprotonation of an aliphatic alcohol. It consists of an alkyl group bonded to an oxygen atom.

As used herein, “aryloxide” or “aryloxy” or “phenoxide” refers to a substituent obtained by deprotonation of an aromatic alcohol. It consists of an aryl group bonded to an oxygen atom.

As used herein, "silyl group" means a linear, branched or cyclic substituent containing 1 to 20 silicon atoms. Silyl groups may contain Si-Si single or double bonds.

For example, expressions such as “C1-C20” and similar forms may refer to a range of carbon atoms, eg, 1 to 20 carbon atoms herein.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a novel and ingenious cascade-type process for the preparation of graft copolymers comprising a polyolefin backbone and one or more polymer side chains and products obtained therefrom, wherein the polymers are controlled by carefully controlled parameters such as polarity. have Polymer side chains can be polar or non-polar.

The essence of the present invention is to use two different olefin monomers in step A), i.e., a first type of olefin monomer and a second type of olefin comonomer having a metal-tuned functional group, thereby directly as catalyst initiators in a subsequent step B). It is to obtain a random copolymer containing short-chain branches having a functional group adjusted with a usable metal, and form a graft copolymer. Accordingly, there is no need to work up, purify or dry the intermediate functional polyolefin, and there is no need to use additional catalysts in the side chain formation step.

The method of the present invention includes at least two steps. During the first step, step A), a polyolefin backbone having one or multiple (eg, multiple) reactive side groups required in step B) as the second step to form the graft copolymer is prepared.

The formation of polymeric side chains can be accomplished by growing these polymeric side chains from metal-adjusted functional short chain branches onto the polyolefin backbone obtained in step A) using a catalytic initiator (grafting from an access object), or by using a catalytic initiator in the step It can be carried out by attaching a pre-synthesized polymer with metal-adjusted functional short-chain branches onto the polyolefin backbone obtained in A).

Step A) relates to polymerizing at least two different types of monomers using a catalyst system to obtain a polyolefin backbone in which metal-adjusted short-chain branches are randomly arranged, one of which has a metal-adjusted functional group. .

The catalyst system used in step A) comprises i) a Group 3-10, preferably Group 3-8 metal catalyst or metal catalyst precursor; and ii) optionally a co-catalyst.

Step B) relates to the formation of polymer side chains from short chain branches on the polyolefin backbone obtained in step A). The polyolefin backbone of step A) above contains functional short chain branches coordinated with one or more metals. In other words, step B) relates to the formation of the graft copolymer.

There are several synthetic routes according to the present invention by which the graft copolymer can be formed during step B). For example, it can be grown via ROP or added via nucleophilic substitution.

In one embodiment, step B) relates to obtaining a graft copolymer and is carried out by ROP of cyclic monomers using metal functional side chain branches on the polyolefin backbone obtained in step A) as catalyst initiators.

In one embodiment, step B) relates to obtaining a graft copolymer, wherein as catalyst initiator is a metal functional side chain branch on the polyolefin backbone obtained in step A) containing at least one carbonyl group-containing functional group, in particular e.g. nucleophilic substitution, in particular for example transesterification, of the polymer to the side chain containing eg carboxylic acid or carbonic acid ester functions.

In one embodiment, step B) relates to obtaining a graft copolymer, carried out by coupling ROP with nucleophilic substitution using the metal functional side chain branch on the polyolefin backbone obtained in step A) as a catalyst initiator. ROP and nucleophilic substitution can be performed simultaneously. Alternatively, nucleophilic substitution is first carried out using a polymer comprising at least one carbonyl group-containing functional group and using the metal functional side chain branch on the polyolefin backbone obtained in step A) as a catalyst initiator to obtain a side chain. ROP is then carried out by adding a cyclic monomer to the metal functional graft copolymer obtained in the first sub-step of step B), which serves as a catalytic initiator for ROP.

Preferably, all of the above steps are performed sequentially and sequentially.

Preferably, processes A) and B) can be carried out without hydrolysis and/or intermediate work-up.

Preferably, the process is carried out in a series of reactors.

Each step will be discussed in more detail below, with specific examples set forth below.

Step A): Polyolefin main chain Produce

The first step of the process according to the invention is the preparation of a polyolefin backbone with reactive electrophilic metal bearing groups. The product obtained in step A) is a metal-adjusted functional side chain-containing polyolefin.

Copolymerization is carried out during step A) of the process of the invention. At least two different olefin monomers are used; One of these is a functional olefin having a heteroatom-containing functional group coordinated with a coordinating metal. This copolymerization reaction leads to random copolymers having functional short chain branches coordinated with one or more metals. The functional short-chain branching coordinated with the metal is the reactive substituent used in step B) to obtain the graft copolymer.

In one embodiment of the present invention, the first type of olefin monomer has the following structure according to Formula I-A:

In the above formula,

C is carbon;

R ^1a , R ^1b , R ^1c , and R ^1d are each independently selected from the group consisting of H or hydrocarbyl of 1 to 16 carbon atoms; or
The first type of olefin monomer is selected from the group consisting of 1-cyclopentene, cyclohexene, norbornene, ethylidene-norbornene, vinylidene-norbornene, and combinations of one or more thereof.

Hydrocarbyl can be, for example, alkyl, alkenyl, alkadienyl and alkynyl. It may also be an alicyclic substituent such as cycloalkyl, cycloalkadienyl, cycloalkenyl. It may also be aromatic substituents, such as monocyclic or polycyclic aromatic substituents, as well as combinations thereof, such as alkyl-substituted aryls and aryl-substituted alkyls. A hydrocarbyl may be substituted with one or more non-hydrocarbyl-containing groups, such as heteroatoms.

Preferably, the olefin monomer according to Formula I-A is ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene , 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, and the group consisting of one or more combinations thereof is selected from Preferably, the first type of olefin monomer is ethylene or propylene.

Also, for example, a combination of ethylene or propylene on the one hand and one or more other olefins on the other hand can be used as the first type of olefin monomer. Substituted analogues of the aforementioned monomers, eg substituted with one or more halogens, may also be used. Also aromatic monomers may be used according to the present invention. It is also possible to use a combination of two or more olefins, such as a combination of ethylene and an α-olefin to reach the LLDPE-side chain.

In one embodiment of the present invention, the second metal-adjusted functional olefin monomer has the following structure according to Formula I-B:

In the above formula,

C is carbon;

R ² , R ³ , and R ⁴ are each independently selected from the group consisting of H or hydrocarbyl of 1 to 16 carbon atoms;

R ⁵ -X-ML _n is a heteroatom-containing functional group coordinated with a metal.

In one embodiment, R ⁵ is absent (in which case R ⁵ -X-ML _n can also be represented as X-ML _n ), or in another embodiment R ⁵ is a hydrocarbylene group. Note that when X is a heteroatom-containing group, the heteroatom is bonded to M.

Preferably, X is

-O-

· -S-

-NR ^6a -

-CO ₂ -

-C(=O)-

-C(=S)S-

-C(=O)S-

-C(=S)O-

-C(=O)N(R ^6a )-

-C(=NR ^6a )O-

-C(=NR ^6a )N(R ^6b )-

-C(=NR ^6b )N(R ^6a )-

-C(=S)N(R ^6a )-

-C(=NR ^6a )S-

-CH ₂ C(R ^6a )=C(OR ^6b )O-

-CH ₂ C(R ^6a )=C(NR ^6b R ^6c )O-

-CH ₂ C(R ^6a )=P(OR ^6b OR ^6c )O-

-C(R ^6a )=N-

-C(R ^6a )R ^6b C(R ^6c )R ^6d O-

-C(R ^6a )R ^6b C(R ^6c )R ^6d NR ^6e -

-C(=O)-R ^6a -C(=O)O-

-C(R ^6b R ^6c )N(R ^6a )-

-S(=O) ₂ O-

-C(R ^6a )(R ^6b )O-

It is a heteroatom or heteroatom-containing group selected from the group consisting of.

Preferably, the heteroatom X in the heteroatom-containing group is O, S, N or a combination of one or more thereof.

Preferably, R ^6a , R ^6b , R ^6c , R ^6d , R ^6e are each independently selected from the group consisting of H or hydrocarbyl of 1 to 16 carbon atoms. Preferably, ML _n is a metal associated with one or more ligands L. Preferably, n is 0, 1, 2 or 3. Here, the total charge on L _n corresponds to the oxidation state of the metal minus one.

M is preferably a coordinating metal selected from the group consisting of magnesium, calcium, boron, aluminum, gallium, bismuth, titanium, zinc, and combinations of one or more thereof.

Preferably, the ligand L is a hydride, hydrocarbyl, halide, alkoxide, aryloxide, amide, thiolate, mercaptate, carboxylate, carbamate, salen, salan, salalen, guanidinate, porphyrin, Independently from the group consisting of β-ketiminates, phenoxy-imines, phenoxy-amines, bisphenolates, trisphenolates, alkoxyamines, alkoxyethers, alkoxythioethers, subcarbonates and subsalicylates or combinations thereof is chosen

In a preferred embodiment, the compound according to Formula I-B is a metal tuned hydroxyl α-olefin or a metal tuned hydroxyl-functional ring constrained cyclic olefin monomer, preferably an aluminum tuned hydroxyl olefin monomer.

A metal-modified hydroxyl α-olefin monomer wherein R ² , R ³ , and R ⁴ are each H, X is -O-, and R ⁵ is -C(R ^7a )(R ^7b )- or a plurality of - C(R ^7a )(R ^7b )-, and R ^7a and R ^7b each independently correspond to H or Formula IB selected from the group consisting of hydrocarbyl of 1 to 16 carbon atoms. An example of an R ⁵ group is -(CH ₂ ) ₉ -.

Metal-modified hydroxy-functional ring-bound cyclic olefins (also referred to as internal olefins) are typically hydroxyl-functional norbornenes, preferably metal-modified 5-norbornene-2-methanol. . This corresponds to Formula IB, wherein R ² and R ⁴ are H, and R ³ and R ⁵ together form a ring structure functionalized with X-ML _n , wherein X is -O-.

Preferably, the metal-adjusted functional olefin monomer is prepared in situ prior to addition of the metal catalyst or metal catalyst precursor. A metal-modified functional olefin monomer can be prepared, for example, by deprotonation reaction of a protic functional olefin monomer according to formula (I-C) with a metal modifier.

[Formula I-C]

In one embodiment, the metal modifier is selected from the metal hydrocarbyl species L _n MR ^7c _p . L, M and n are as defined above. R ^7c is hydride or hydrocarbyl of 1 to 16 carbon atoms, and p is 1, 2 or 3; where the total charge of L _n + R ^7c _p corresponds to the oxidation state of the metal.

Preferably, the metal modifier is mono-, di- or trihydrocarbyl aluminum, mono-, di- or trihydrocarbyl boron, mono-, di- or trihydrocarbyl gallium, mono-, di- or trihydrocarbyl gallium, mono-, di- or trihydrocarbyl bismuth, mono- or dihydrocarbyl zinc, mono- or dihydrocarbyl magnesium, mono- or dihydrocarbyl calcium, mono-, di-, tri- or tetrahydrocarbyl titanium and one It is a combination of the above.

Preferably, the metal regulator is trimethyl aluminum, triethyl aluminum, tri(i-propyl) aluminum, tri(n-butyl) aluminum, tri(i-butyl) aluminum (TIBA), tri(t-butyl) aluminum, Tri(n-hexyl) aluminum, tri(n-octyl) aluminum, di(i-butyl) aluminum hydride (DIBALH), dimethyl aluminum 2,6-di(t-butyl)-4-methyl-phenoxide, di Ethyl aluminum 2,6-di(t-butyl)-4-methyl-phenoxide, di(i-butyl) aluminum 2,6-di(t-butyl)-4-methyl-phenoxide, i-butyl aluminum- Bis(di-trimethylsilyl)amide), n-octyl aluminum-di(pyridine-2-methoxide), bis(n-octadecyl)-i-butyl aluminum, i-butyl aluminum-bis(di(n-pentyl )amide), n-octyl aluminum-bis(2,6-di-t-butylphenoxide), n-octyl aluminum-di-ethyl(1-naphthyl)amide), ethyl aluminum-bis(t-butyldimethyl siloxide), ethyl aluminum-di(bis(trimethylsilyl)amide), ethyl aluminum-bis(2,3,6,7-dibenzo-1-azacycloheptane-amide), n-octyl aluminum-bis(2 ,3,6,7-dibenzo-1-azacycloheptane-amide), n-octyl-aluminum-bis(dimethyl(t-butyl)siloxide, trimethyl gallium, triethyl gallium, tri(i-butyl) gallium , di-n-butyl magnesium (DBM), dimethyl magnesium, butyl-octyl-magnesium, butyl-ethyl-magnesium, butyl magnesium 2,6-di(t-butyl)-4-methyl-phenoxide, benzyl calcium 2, 6-di(t-butyl)-4-methyl-phenoxide, methyl zinc 2,6-di(t-butyl)-4-methyl-phenoxide, diethyl zinc (DEZ), dimethyl zinc, di-isopropyl Zinc, di-t-butyl zinc, di-(n-hexyl) zinc, ethyl zinc (t-butoxide), ethyl zinc 2,6-di(t-butyl)-4-methyl-phenoxide, trimethyl boron, tributyl boron, diethyl boron 2,6-di(t-butyl)-4-methyl-phenoxide, 9-borabicyclo(3.3.1)nonane, catecholborane and diborane.

In one embodiment, the metal modifier is selected from the group consisting of TIBA, DIBALH, DBM, DEZ.

It should be noted that the metal modifier may also act as a chain transfer agent during the polymerization of step (A).

Catalyst systems suitable for use in step A)

The catalyst system for use in step A) comprises the following components:

i) a metal catalyst or metal catalyst precursor comprising a metal of groups 3-10 of the IUPAC Periodic Table of Elements;

ii) optionally a co-catalyst;

iii) optionally a scavenger.

Suitable metal catalysts and/or catalytic metal precursors are discussed in this section as well as any suitable co-catalysts. The metal catalyst for step A) requires a co-catalyst to achieve real catalytic activity.

Metal catalyst or catalyst precursor suitable for step A)

In the following section some examples of metal catalysts or metal catalyst precursors that can be used to prepare metal catalysts according to the present invention are listed. A metal catalyst suitable for use in step A) of the present invention can be obtained by reacting a metal catalyst precursor with a co-catalyst prior to use in step A) or by reacting the metal catalyst precursor with a co-catalyst in situ.

In the present invention, the metal catalyst is a Group 3 metal, a Group 4 metal, a Group 5 metal, a Group 6 metal, a Group 7 metal, a Group 8 metal, a Group 9 metal or a Group 10 metal, preferably Y, Ti, Zr, Hf , has a metal center selected from V, Cr, Fe, Co, Ni, Pd

In the present invention, the metal catalyst or metal catalyst precursor may be, for example, a single site catalyst or a Ziegler-Natta catalyst.

As used herein, the Ziegler-Natta catalyst includes a transition metal halide selected from titanium halides, chromium halides, hafnium halides, zirconium halides, and vanadium halides supported on a metal or metalloid compound (such as a magnesium compound or a silica compound). means a transition metal-containing solid catalyst compound that An overview of catalysts of this type is for example [T. Pullukat and R. Hoff in Catal. Rev. -Sci. Eng. 41, vol. 3 and 4, 389-438, 1999]. The preparation of the procatalyst is disclosed, for example, in WO96/32427 A1. US2009/0048399, US2014/0350200, WO96/32427, WO01/23441, WO2007/134851, US4978648, EP1283 222A1, US5556820; US4414132; The Ziegler-Natta catalysts reported in US5106806 and US5077357 may also be suitable for use as metal catalyst precursors in the present invention.

The metal catalyst or metal catalyst precursor is for example a C _s -, C ₁ - or C ₂ -symmetric zirconium or hafnium metallocene, preferably an indenyl substituted zirconium or hafnium dihalide, more preferably a bridging bis- indenyl zirconium or hafnium dihalide, even more preferably rac -dimethylsilyl bis-indenyl zirconium or hafnium dichloride ( rac -Me ₂ Si(Ind) ₂ ZrCl ₂ and rac -Me ₂ Si(Ind) ₂ HfCl, respectively) ₂ ), or rac -dimethylsilyl bis-(2-methyl-4-phenyl-indenyl) zirconium or hafnium dichloride ( rac -Me ₂ Si(2-Me-4-Ph-Ind) ₂ ZrCl ₂ and rac respectively -Me ₂ Si(2-Me-4-Ph-Ind) ₂ HfCl ₂ ).

In the present invention, the catalyst precursor is, for example, a so-called half-metallocene, or constrained structure catalyst, even more preferably, C ₅ Me ₅ [(C ₆ H ₁₁ ) ₃ P=N]TiCl ₂ , [ Me ₂ Si(C ₅ Me ₄ )N(tBu)]TiCl ₂ , [C ₅ Me ₄ (CH ₂ CH ₂ NMe ₂ ]TiCl ₂ ).

In the present invention, the catalyst is for example a so-called post-metallocene, preferably [Et ₂ NC(N(2,6-iPr ₂ -C ₆ H ₃ )]TiCl ₃ or [N-(2, 6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium dimethyl.

The metal catalyst or metal catalyst precursor may also be, for example, preferably of the formula (C ₅ R ⁸ ₄ )R ⁹ (C ₁₃ R ⁸ ₈ )ML ¹ _n (wherein C ₅ R ⁸ ₄ is unsubstituted or substituted cyclo). pentadienyl, C ₁₃ R ¹¹ ₈ is an unsubstituted fluorenyl group or a substituted fluorenyl group; the bridging R ⁹ group is -Si(Me) ₂ -, -Si(Ph) ₂ -, -C(Me) ₂ - or -C (Ph) ₂ -, thus yielding C ₁ - _and C _{s -symmetric} metallocenes ) .

Non-limiting examples of suitable zirconocene dichloride metal catalyst precursors for use in the present invention include bis(cyclopentadienyl) zirconium dichloride, bis(methyl-cyclopentadienyl) zirconium dichloride, bis(n-propyl -cyclopentadienyl) zirconium dichloride, bis(n-butyl-cyclopentadienyl) zirconium dichloride, bis(1,3-dimethyl-cyclopentadienyl) zirconium dichloride, bis(1,3-di- t-Butyl-cyclopentadienyl) zirconium dichloride, bis(1,3-ditrimethylsilyl-cyclopentadienyl) zirconium dichloride, bis(1,2,4-trimethyl-cyclopentadienyl) zirconium dichloride , bis(1,2,3,4-tetramethyl-cyclopentadienyl) zirconium dichloride, bis(pentamethylcyclopentadienyl) zirconium dichloride, bis(indenyl) zirconium dichloride, bis(2-phenyl -indenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, bis (tetrahydrofluorenyl) zirconium dichloride, dimethylsilyl-bis (cyclopentadienyl) zirconium dichloride, dimethylsilyl-bis (3 -t-butyl-cyclopentadienyl) zirconium dichloride, dimethylsilyl-bis (3-trimethylsilyl-cyclopentadienyl) zirconium dichloride, dimethylsilyl-bis (tetrahydrofluorenyl) zirconium dichloride, dimethylsilyl -(1-indenyl)(cyclopentadienyl) zirconium dichloride, dimethylsilyl-(1-indenyl)(fluorenyl) zirconium dichloride, dimethylsilyl-(1-indenyl)(octahydrofluorenyl) ) zirconium dichloride, rac-dimethylsilyl-bis(2-methyl-3-t-butyl-cyclopentadienyl) zirconium dichloride, rac-dimethylsilyl-bis(1-indenyl) zirconium dichloride, rac-dimethyl Silyl-bis(4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, rac-dimethylsilyl-bis(2-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilyl-bis (4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilyl-bis(2-methyl-4-phenyl-1-indenyl) zirconium dichloride Rolide, rac-ethylene-bis(1-indenyl) zirconium dichloride, rac-ethylene-bis(4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, rac-1,1, 2,2-tetramethylsilanylene-bis(1-indenyl) zirconium dichloride, rac-1,1,2,2-tetramethylsilanylene-bis(4,5,6,7-tetrahydro-1- indenyl) zirconium dichloride, rac-ethylidene (1-indenyl) (2,3,4,5-tetramethyl-1-cyclopentadienyl) zirconium dichloride, rac-[1-(9-fluorene Nyl)-2-(2-methylbenzo[b]indeno[4,5-d]thiophen-1-yl)ethane]zirconium dichloride, dimethylsilyl bis(cyclopenta-phenanthren-3-ylidene) Zirconium dichloride, dimethylsilyl bis(cyclopenta-phenanthren-1-ylidene) Zirconium dichloride, dimethylsilyl bis(2-methyl-cyclopenta-phenanthren-1-ylidene) zirconium dichloride, dimethylsilyl bis( 2-methyl-3-benz-inden-3-ylidene) zirconium dichloride, dimethylsilyl-bis[(3a,4,5,6,6a)-2,5-dimethyl-3-(2-methylphenyl)- 6H-cyclopentatien-6-ylidene] zirconium dichloride, dimethylsilyl-(2,5-dimethyl-1-phenylcyclopenta[b]pyrrol-4(1H)-ylidene)(2-methyl-4- Phenyl-1-indenyl) zirconium dichloride, bis(2-methyl-1-cyclopenta-phenanthren-1-yl) zirconium dichloride, [ortho-bis(4-phenyl-2-indenyl)benzene] zirconium Dichloride, [ortho-bis(5-phenyl-2-indenyl)benzene] zirconium dichloride, [ortho-bis(2-indenyl)benzene] zirconium dichloride, [ortho-bis (1-methyl-2- indenyl) benzene] zirconium dichloride, [2,2'-(1,2-phenyldiyl)-1,l'-dimethylsilyl-bis(indenyl)] zirconium dichloride, [2,2'-(1 ,2-phenyldiyl)-1,1'-(1,2-ethanediyl)-bis(indenyl)] zirconium dichloride, dimethylsilyl-(cyclopentadienyl)(9-fluorenyl) zirconium dichloride , diphenylsilyl- (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylmethylene- (cyclophene Tadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene- (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylmethylene- (cyclopentadienyl) (octahydrofluorenyl) zirconium dichloride Chloride, diphenylmethylene- (cyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, dimethylmethylene- (cyclopentadienyl) (2,7-di-t-butyl-fluorenyl) zirconium dichloride , Diphenylmethylene-(cyclopentadienyl)(2,7-di-t-butyl-fluorenyl) zirconium dichloride, dimethylmethylene-(3-methyl-1-cyclopentadienyl)(fluorenyl) Zirconium dichloride, diphenylmethylene- (3-methyl-1-cyclopentadienyl) (fluorenyl) Zirconium dichloride, dimethylmethylene- (3-cyclohexyl-1-cyclopentadienyl) (fluorenyl) Zirconium dichloride, diphenylmethylene-(3-cyclohexyl-1-cyclopentadienyl)(fluorenyl) zirconium dichloride, dimethylmethylene-(3-t-butyl-1-cyclopentadienyl)(fluorenyl) Nyl) zirconium dichloride, diphenylmethylene- (3-t-butyl-1-cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylmethylene- (3-adamantyl-1-cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene- (3-adamantyl-1-cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylmethylene- (3-methyl-1-cyclopentadienyl) )(2,7-di-t-butyl-fluorenyl) zirconium dichloride, diphenylmethylene-(3-methyl-1-cyclopentadienyl)(2,7-di-t-butyl-fluorenyl ) Zirconium dichloride, dimethylmethylene-(3-cyclohexyl-1-cyclopentadienyl)(2,7-di-t-butyl-fluorenyl) zirconium dichloride, diphenylmethylene-(3-cyclohexyl- 1-cyclopentadienyl)(2,7-di-t-butyl-fluorenyl) zirconium dichloride, dimethylmethylene-(3-t-butyl-1-cyclopentadienyl)(2,7-di- t-butyl-fluorenyl) zirconium dichloride, diphenylmethylene-(3-t-butyl-1-cyclopentadienyl)(2,7-di-t-butyl-fluorenyl) zirconium dichloride, dimethyl methylene- (3-methyl-cyclopentadienyl)(octahydro-octamethyl-dibenzo-fluorenyl) zirconium dichloride, diphenylmethylene-(3-methyl-cyclopentadienyl)(octahydro-octamethyl-di Benzo-fluorenyl) zirconium dichloride, dimethylmethylene- (3-cyclohexyl-cyclopentadienyl) (octahydro-octamethyl-dibenzo-fluorenyl) zirconium dichloride, diphenylmethylene- (3-cyclo Hexyl-cyclopentadienyl) (octahydro-octamethyl-dibenzo-fluorenyl) zirconium dichloride, dimethylmethylene- (3-t-butyl-cyclopentadienyl) (octahydro-octamethyl-dibenzo- Fluorenyl) zirconium dichloride, diphenylmethylene- (3-t-butyl-cyclopentadienyl) (octahydro-octamethyl-dibenzo-fluorenyl) zirconium dichloride, dimethylmethylene- (3-adamane Tyl-cyclopentadienyl) (octahydro-octamethyl-dibenzo-fluorenyl) zirconium dichloride, diphenylmethylene- (3-adamantyl-cyclopentadienyl) (octahydro-octamethyl-dibenzo -fluorenyl) zirconium dichloride.

In a preferred embodiment, the metal catalyst or metal catalyst precursor is, for example, [[2,2'-[[[2-(dimethylamino-kN)ethyl]imino-kN]bis(methylene)]bis[4, 6-bis(1,1-dimethylethyl)phenolato-kO]] zirconium dibenzyl, (phenylmethyl)[[2,2'-[(propylimino-kN)bis(methylene)]bis[4,6 -bis(1,1-dimethylethyl)phenolato-kO]] zirconium dibenzyl or (phenylmethyl)[[2,2'-[[[(2-pyridinyl-kN)methyl]imino-kN]bis (methylene)]bis[4,6-bis(1,1-dimethylethyl)phenolato-kO]] zirconium dibenzyl.

In a preferred embodiment, the complexes reported in WO 00/43426, WO 2004/081064, US 2014/0039138 A1, US 2014/0039139 A1 and US 2014/0039140 A1 are used as metal catalyst precursors in the process of the present invention. suitable for use as

Compounds similar to those listed above in which Zr is replaced by Hf, so-called hafnocenes, can also be used as catalyst precursors according to the present invention.

Metal catalysts or metal catalyst precursors for use in the present invention may also be by post-metallocene catalysts or catalyst precursors.

In a preferred embodiment, the metal catalyst or metal catalyst precursor is [HN(CH ₂ CH ₂ N-2,4,6-Me ₃ -C ₆ H ₂ ) ₂ ]Hf(CH ₂ Ph) ₂ or bis[N,N '-(2,4,6-trimethylphenyl)amido)ethylenediamine]hafnium dibenzyl.

In another preferred embodiment, the metal catalyst or metal catalyst precursor is 2,6-diisopropylphenyl-N-(2-methyl-3-(octylimino)butane-2) hafnium trimethyl, 2,4,6-tri Methylphenyl-N-(2-methyl-3-(octylimino)butane-2) hafnium trimethyl.

In a preferred embodiment, the metal catalyst or metal catalyst precursor is [2,6-iPr ₂ C ₆ H ₃ NC(2-iPr-C ₆ H ₄ )-2-(6-C ₅ H ₆ )]HfMe ₂ - [ N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium dimethyl .

Another non-limiting example of a metal catalyst precursor according to the present invention is [N-(2,6-di(1-methylethyl)phenyl)amido)(o-tolyl)(α-naphthalene-2-diyl(6- Pyridin-2-diyl)methane)] hafnium dimethyl, [N-(2,6-di(1-methylethyl)phenyl)amido)(o-tolyl)(α,α-naphthalene-2-diyl(6- Pyridin-2-diyl)methane)] hafnium di(N,N-dimethylamido), [N-(2,6-di(l-methylethyl)phenyl)amido)(o-tolyl)(α,α -naphthalene-2-diyl (6-pyridin-2-diyl) methane)] hafnium dichloride, [N- (2,6-di (1-methylethyl) phenyl) amido) (phenanthren-5-yl) (α,α-naphthalen-2-diyl (6-pyridin-2-diyl)methane)] hafnium dimethyl, [N-(2,6-di(1-methylethyl)phenyl)amido)(phenanthrene-5 -yl)(α-naphthalen-2-diyl(6-pyridine 2-diyl)methane)] hafnium di(N,N-dimethylamido), [N-(2,6-di(1-methylethyl)phenyl) )amido)(phenanthren-5-yl) (α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)] hafnium dichloride. Other non-limiting examples include the family of pyridyl diamide metal dichloride complexes: [N-[2,6-bis(1-methylethyl)phenyl]-6-[2-[phenyl(phenylamino -kN)methyl]phenyl]-2-pyridinemethanamineto(2-)-kN1,kN2]hafnium dichloride, [N-[2,6-bis(1-methylethyl)phenyl]-6-[2 -[(phenylamino-kN)methyl]-1-naphthalenyl]-2-pyridinemethanamineto(2-)-kN1,kN2] hafnium dichloride, [N-[2,6-bis(1-) methylethyl)phenyl]-α-[2-(1-methylethyl)phenyl]-6-[2-[(phenylamino-kN)methyl]phenyl]-2-pyridinemethanamineto(2-)-kN1 ,kN2] hafnium dichloride, [N-(2,6-diethylphenyl)-6-[2-[phenyl(phenylamino-kN)methyl]-1-naphthalenyl]-2-pyridinemethanamineto (2-)-kN1,kN2]zirconium dichloride, [4-methyl-2-[[2-phenyl-1-(2-pyridinyl-kN)ethyl]amino-kN]phenolato(2-)-kO ]bis(phenylmethyl)hafnium bis(phenylmethyl), [2-(1,1-dimethylethyl)-4-methyl-6-[[2-phenyl-1-(2-pyridinyl-kN)ethyl]amino -kN]phenolato(2-)-kO] hafnium bis(phenylmethyl), [2-(1,1-dimethylethyl)-4-methyl-6-[[phenyl(2-pyridinyl-kN)methyl] Amino-kN]phenolato(2-)-kO]hafnium bis(phenylmethyl).

Non-limiting examples of suitable titanium dichloride metal catalyst precursors for use in the present invention include cyclopentadienyl (P,P,P-tri-t-butylphosphine imidato) titanium dichloride, pentafluorophenylcyclopenta Dienyl (P, P, P-tri-t-butylphosphine imidato) titanium dichloride, pentamethylcyclopentadienyl (P, P, P-tri-t-butylphosphine imidato) titanium dichloride, 1,2,3,4-tetraphenyl-cyclopentadienyl (P,P,P-tri-t-butylphosphine imideto) titanium dichloride, cyclopentadienyl (P,P,P-tricyclohexyl Phosphine Imidato) Titanium Dichloride, Pentafluorophenyl Cyclopentadienyl (P,P,P-Tricyclohexylphosphine Imidato) Titanium Dichloride, Pentamethylcyclopentadienyl (P,P,P-Tricyclohexylphosphine Imidato) Cyclohexylphosphine imideto) titanium dichloride, 1,2,3,4-tetraphenyl-cyclopentadienyl (P,P,P-tricyclohexylphosphine imideto) titanium dichloride, pentamethylcyclopentadier Nyl(P,P-dicyclohexyl-P-(phenylmethyl)phosphine imidato) titanium dichloride, cyclopentadienyl(2,6-di-t-butyl-4-methylphenoxy) titanium dichloride, Pentafluorophenylcyclopentadienyl (2,6-di-t-butyl-4-methylphenoxy) titanium dichloride, pentamethylcyclopentadienyl (2,6-di-t-butyl-4-methylphenoxy) C) titanium dichloride, 1,2,3-trimethyl-cyclopentadienyl (2,6-bis (1-methylethyl) phenolato) titanium dichloride, [(3a,4,5,6,6a-η -2,3,4,5,6-pentamethyl-3aH-cyclopenta[b]thien-3a-yl](2,6-bis(1-methylethyl)phenolato) titanium dichloride, pentamethylcyclopenta Dienyl (N,N'-bis(1-methylethyl)ethaneimidiamidato) titanium dichloride, pentamethylcyclopentadienyl (N,N'-dicyclohexylbenzenecarboximidateto) titanium dichloride , Pentamethylcyclopentadienyl (N, N'-bis (1-methylethyl) benzenecarboximidamidateto) titanium dichloride, cyclopentadienyl (1,3-bis (1,1-dimethylethyl) - 2 - this Midazolidiniminato) Titanium Dichloride, Cyclopentadienyl (1,3-dicyclohexyl-2-imidazolidineiminato) Titanium Dichloride, Cyclopentadienyl (1,3-bis[2 ,6-bis(1-methylethyl)phenyl]-2-imidazolidiniminato)titanium dichloride, pentafluorophenylcyclopentadienyl(1,3-bis(1,1-dimethylethyl)- 2-Imidazolidiniminato) Titanium Dichloride, Pentafluorophenylcyclopentadienyl (1,3-dicyclohexyl-2-imidazolidiniminato) Titanium Dichloride, Pentafluorophenylcyclo Pentadienyl (1,3-bis [2,6-bis (1-methylethyl) phenyl] -2-imidazolidiniminato) titanium dichloride, pentamethylcyclopentadienyl (di-t-butyl ketimino) titanium dichloride, pentamethylcyclopentadienyl (2,2,4,4-tetramethyl-3-pentaniminato) titanium dichloride, [(3a,4,5,6,6a-η )-2,4,5,6-tetramethyl-3aH-cyclopenta[b]thien-3a-yl](2,2,4,4-tetramethyl-3-pentaniminato) titanium dichloride, cyclo Pentadienyl (N,N-bis(1-methylethyl)benzenecarboximidamidateto) Titanium Dichloride, Pentafluorophenylcyclopentadienyl (N,N-bis(1-methylethyl)benzenecarboximide amidato) titanium dichloride, pentamethylcyclopentadienyl (N, N-bis (1-methylethyl) benzenecarboximidamidate) titanium dichloride, cyclopentadienyl (2,6-difluoro-N ,N-bis(1-methylethyl)benzenecarboximidiamidato)titanium dichloride,pentafluorophenylcyclopentadienyl(2,6-difluoro-N,N-bis(1-methylethyl)benzene Carboximidamidateto) Titanium Dichloride, Pentamethylcyclopentadienyl (2,6-difluoro-N,N-bis(1-methylethyl)benzenecarboximidateto) Titanium Dichloride, Cyclopentadie Nyl(N,N-dicyclohexyl-2,6-difluorobenzenecarboximidamidateto) titanium dichloride, pentafluorophenylcyclopentadienyl(N,N-dicyclohexyl-2,6-di fluorobenzenecarboximidiamidato) titanium dichloride, pentamethylcyclopentadi Enyl (N,N-dicyclohexyl-2,6-difluorobenzenecarboximidamidateto) titanium dichloride, cyclopentadienyl (N,N,N',N'-tetramethylguanidinato ) Titanium dichloride, pentafluorophenylcyclopentadienyl (N, N, N', N'-tetramethylguanidinato) Titanium dichloride, pentamethylcyclopentadienyl (N, N, N', N'-tetramethylguanidinato) titanium dichloride, pentamethylcyclopentadienyl (1-(imino)phenylmethyl)piperidinato) titanium dichloride, pentamethylcyclopentadienyl chromium dichloride tetra Includes hydrofuran complexes.

Non-limiting examples of titanium (IV) dichloride metal catalysts suitable for use in the present invention include (N-t-butylamido)(dimethyl)(tetramethylcyclopentadienyl)silane titanium dichloride, (N-phenylamido )(dimethyl)(tetramethylcyclopentadienyl)silane titanium dichloride, (N-sec-butylamido)(dimethyl)(tetramethylcyclopentadienyl)silane titanium dichloride, (N-sec-dodecylami Figure) (dimethyl) (fluorenyl) silane titanium dichloride, (3-phenylcyclopentadien-1-yl) dimethyl (t-butylamido) silane titanium dichloride, (3- (pyrrol-I-yl) Cyclopentadien-1-yl) dimethyl (t-butylamido) silane titanium dichloride, (3,4-diphenylcyclopentadien-1-yl) dimethyl (t-butylamido) silane titanium dichloride, 3 -(3-N,N-dimethylamino)phenyl)cyclopentadien-1-yl)dimethyl(t-butylamido)silane titanium dichloride, (P-t-butylphospho)(dimethyl) (tetramethylcyclopentadiene nyl)silane titanium dichloride. Another example is when Ln is dimethyl, dibenzyl, diphenyl, 1,4-diphenyl-2-butene-1,4-diyl, 1,4-dimethyl-2-butene-1,4-diyl or 2,3-dimethyl There is a metal catalyst precursor listed immediately above that is -2-butene-1,4-diyl.

Suitable metal catalyst precursors may also be trivalent transition metals such as those described in WO 9319104 (eg see in particular Example 1, page 13, line 15).

Suitable metal catalyst precursors are also [C5Me4CH2CH2N(n-Bu)2]TiCl2 described in WO 9613529 (see eg especially Example III, page 20, lines 10-13) or WO 97142232 and WO 9742236 (eg For example, it may be a trivalent transition metal such as [C5H(iPr)3CH2CH2NMe2]TiCl2 described in Example 1, page 26, line 14).

In one embodiment, the metal catalyst precursor is [C5H4CH2CH2NMe2]TiCl2.

In one embodiment, the metal catalyst or metal catalyst precursor is also [C5Me4CH2CH2NMe2]TiCl2, [C5H4CH2CH2NiPr2]TiCl2, [C5Me4CH2CH2NiPr2]TiCl2, [C5H4C9H6N]TiCl2, [C5H4CH2CH2NMe2]CrCl2, [C5Me4CH2CH2NMe2]CrCl2; [C5H4CH2CH2NiPr2]CrCl2, [C5Me4CH2CH2NiPr2]CrCl2 or [C5H4C9H6N]CrCl2.

A non-limiting list of examples of suitable metal catalyst precursors according to the present invention is as follows: (N,N-dimethylamino)methyl-tetramethylcyclopentadienyl titanium dichloride, (N,N-dimethylamino)ethyl- Tetramethylcyclopentadienyl titanium dichloride, (N,N-dimethylamino)propyl-tetramethylcyclopentadienyl titanium dichloride, (N,N dibutylamino)ethyl-tetramethylcyclopentadienyl titanium dichloride, (pyrrolidinyl)ethyl-tetramethylcyclopentadienyl titanium dichloride, (N,N-dimethylamino)ethyl-fluorenyl titanium dichloride, (bis(1-methyl-ethyl)phosphino)ethyl-tetramethyl Cyclopentadienyl titanium dichloride, (bis(2-methyl-propyl)phosphino)ethyl-tetramethylcyclopentadienyl titanium dichloride, (diphenylphosphino)ethyl-tetramethylcyclopentadienyl titanium dichloride, (Diphenylphosphino)methyldimethylsilyl-tetramethylcyclopentadienyl titanium dichloride. Another example is Ln, wherein chloride is bromide, hydride, methyl, benzyl, phenyl, allyl, (2-N,N-dimethylaminomethyl)phenyl, (2-N,N-dimethylamino)benzyl, 2,6- dimethoxyphenyl, pentafluorophenyl, and/or catalysts listed immediately above in which the metal is trivalent titanium or trivalent chromium.

In a preferred embodiment, the catalyst precursor is [2-(2,4,6-iPr3-C6H2)-6-(2,4,6-iPr3-C6H2)-C5H3N]Ti(CH2Ph)3 or [Et2NC(N- 2,6-iPr2-C6H3)2]TiCl3.

Other non-limiting examples of metal catalyst precursors according to the present invention are: {N',N"-bis[2,6-di(1-methylethyl)phenyl]-N,N-diethylguanidi nato} titanium trichloride, {N',N"-bis[2,6-di(1-methylethyl)phenyl]-N-methyl-N-cyclohexylguanidinato} titanium trichloride, {N ',N"-bis[2,6-di(1-methylethyl)phenyl]-N,N-pentamethyleneguanidinato}titanium trichloride, {N',N"-bis[2,6- Di(methyl)phenyl]-sec-butyl-amidinato} titanium trichloride, {N-trimethylsilyl,N'-(N",N"-dimethylaminomethyl)benzamidinato} titanium dichloride THF Complex, {N-trimethylsilyl, N'-(N",N"-dimethylaminomethyl)benzamidinato} vanadium dichloride THF complex, {N,N'-bis(trimethylsilyl)benzamidinato } Titanium dichloride THF complex, {N,N'-bis(trimethylsilyl)benzamidinato} vanadium dichloride THF complex.

In a preferred embodiment, the catalyst precursor is for example [C5H3N{CMe=N(2,6-iPr2C6H3)}2]FeCl2, [2,4-(t-Bu)2,-6-(CH=NC6F5)C6H2O ]2TiCl2 or bis[2-(1,1-dimethylethyl)-6-[(pentafluorophenylimino)methyl]phenolato]titanium dichloride. Other non-limiting examples of metal catalyst precursors according to the present invention are for example bis[2-[(2-pyridinylimino)methyl]phenolato]titanium dichloride, bis[2-(1,1-dimethylethyl )-6-[(phenylimino)methyl]phenolato]titanium dichloride, bis[2-(1,1-dimethylethyl)-6-[(1-naphthalenylimino)methyl]phenolato]titanium dichloride, bis[3-[(phenylimino)methyl][1,1'-biphenyl]-2-phenolato]titanium dichloride, bis[2-(1,1-dimethylethyl)-4-methyl Toxy-6-[(phenylimino)methyl]phenolato]titanium dichloride, bis[2,4-bis(1-methyl-1-phenylethyl)-6-[(phenylimino)methyl]phenolato] Titanium dichloride, bis[2,4-bis(1,1-dimethylpropyl)-6-[(phenylimino)methyl]phenolato]titanium dichloride, bis[3-(1,1-dimethylethyl)- 5-[(phenylimino)methyl][1,1'-biphenyl]-4-phenolato]titanium dichloride, bis[2-[(cyclohexylimino)methyl]-6-(1,1- dimethylethyl)phenolato]titanium dichloride, bis[2-(1,1-dimethylethyl)-6-[[[2-(1-methylethyl)phenyl]imino]methyl]phenolato]titanium dichloride, Bis[2-(1,1-dimethylethyl)-6-[(pentafluorophenylimino)ethyl]phenolato]titanium dichloride, bis[2-(1,1-dimethylethyl)-6-[( Pentafluorophenylimino)propyl]phenolato]titanium dichloride, Bis[2,4-bis(1,1-dimethylethyl)-6-[1-(phenylimino)ethyl]phenolato]titanium dichloride , bis[2,4-bis(1,1-dimethylethyl)-6-[1-(phenylimino)propyl]phenolato]titanium dichloride, bis[2,4-bis(1,1-dimethylethyl) )-6-[phenyl(phenylimino)methyl]phenolato]titanium dichloride. Another example is that the dichloride is dimethyl, dibenzyl, diphenyl, 1,4-diphenyl-2-butene-1,4-diyl, 1,4-dimethyl-2-butene-1,4-diyl or 2,3 -Dimethyl-2-butene-1,4-diyl may be substituted, and/or the metal may be zirconium or hafnium, a metal catalyst precursor listed immediately above in the list.

In a preferred embodiment, the catalyst precursor is [2-[[[2-[[[3,5-bis(1,1-dimethylethyl)-2-(hydroxy-kO)phenyl]methyl]amino-kN]ethyl ]methylamino-kN]methyl]-4,6-bis(1,1-dimethylethyl)phenolato(2-)-kO]titanium bis(phenylmethyl), [2,4-dichloro-6-[[[ 2-[[[3,5-dichloro-2-(hydroxy-kO)phenyl]methyl]amino-kN]ethyl]methylamino-kN]methyl]phenolato(2-)-kO]titanium bis(phenylmethyl ), [2-[[[[1-[[2-(hydroxy-kO)-3,5-diiodophenyl]methyl]-2-pyrrolidinyl-kN]methyl]amino-kN]methyl] -4-methyl-6-tricyclo[3.3.1.13,7]dec-1-ylphenolato(2-)-kO]titanium bis(phenylmethyl), [2-[[[2-[[[[2 -(hydroxy-kO)-3,5-bis(1-methyl-1-phenylethyl)phenyl]methyl]methylamino-kN]methyl]phenyl]methylamino-kN]methyl]-4,6-bis( 1-methyl-1-phenylethyl)phenolato(2-)-kO]titanium bis(phenylmethyl), [2,4-dichloro-6-[[[2-[[[[3,5-dichloro-2 -(hydroxy-kO)phenyl]methyl]amino-kN]methyl]phenyl]amino-kN]methyl]phenolato(2-)-kO]titanium bis(phenylmethyl). Another example is bis(phenylmethyl) dichloride, dimethyl, diphenyl, 1,4-diphenyl-2-butene-1,4-diyl, 1,4-dimethyl-2-butene-1,4-diyl or 2 There are metal catalyst precursors listed in the list immediately above that can be replaced by ,3-dimethyl-2-butene-1,4-diyl and/or the metal can be zirconium or hafnium.

A non-limiting list of examples of chromium catalysts suitable for use in the present invention is as follows: (N-t-butylamido)(dimethyl)(tetramethylcyclopentadienyl)silane chromium bis(trimethylsilyl)methyl, (N -phenylamido)(dimethyl)(tetramethylcyclopentadienyl)silane chromium bis(trimethyl)methyl, (N-sec-butylamido)(dimethyl)(tetramethylcyclopentadienyl)silane chromium bis(trimethylsilyl) )methyl, (N-sec-dodecylamido)(dimethyl)(fluorenyl)silane chromium hydride triphenylphosphine, (P-t-butylphospho)(dimethyl)(tetramethylcyclopentadienyl)silane chromium Bis(trimethylsilyl)methyl. Other examples include those in which L1 is hydride, methyl, benzyl, phenyl, allyl, (2-N,N-dimethylaminomethyl)phenyl, (2-N,N-dimethylamino)benzyl; ie, chromium methyl, chromium benzyl, chromium allyl, chromium (2-N,N-dimethylamino)benzyl and/or the catalysts listed immediately above where the metal is trivalent yttrium or samarium. Another example is that L1 is chloride, bromide, hydride, methyl, benzyl, phenyl, allyl, (2-N,N-dimethylaminomethyl)phenyl, (2-N,N-dimethylamino)benzyl, and/or a metal A catalyst listed immediately above that is trivalent titanium or trivalent chromium.

Non-limiting examples of metal catalyst precursors according to the present invention are: N,N'-1,2-acenaphthylenediylidenebis(2,6-bis(1-methylethyl)benzenamine) nickel di bromide, N,N'-1,2-ethanediylidenebis(2,6-dimethylbenzenamine) nickel dibromide, N,N'-1,2-ethanediylidenebis(2,6-bis( 1-methyl-ethyl)benzenamine) nickel dibromide, N,N'-1,2-acenaphthylenediylidenebis(2,6-dimethylbenzenamine) nickel dibromide, N,N'-1,2 -Acenaphthylenediylidenebis(2,6-bis(1-methylethyl)benzenamine) nickel dibromide, N,N'-1,2-acenaphthylenediylidenebis(1,1'-bi Phenyl)-2-amine nickel dibromide. Another example is the catalysts listed immediately above in which the bromide may be replaced by chloride, hydride, methyl, benzyl and/or the metal may be palladium.

Further non-limiting examples of metal catalyst precursors according to the present invention are: [2-[[[2,6-bis(1-methylethyl)phenyl]imino-kN]methyl]-6-(1 ,1-dimethylethyl)phenolato-kO] nickel phenyl(triphenylphosphine), [2-[[[2,6-bis(1-methylethyl)phenyl]imino-kN]methyl]-6-( 1,1-dimethylethyl)phenolato-kO] nickel phenyl(triphenylphosphine), [2-[[[2,6-bis(1-methylethyl)phenyl]imino-kN]methyl]phenolato- kO] nickel phenyl(triphenylphosphine)-, [3-[[[2,6-bis(1-methylethyl)phenyl]imino-kN]methyl][1,1'-biphenyl]-2- oleato-kO] nickel phenyl(triphenylphosphine)-, [2-[[[2,6-bis(1-methylethyl)phenyl]imino-kN]methyl]-4-methoxyphenolate-kO ] nickel phenyl (triphenylphosphine), [2-[[[2,6-bis (1-methylethyl) phenyl] imino-kN] methyl] -4-nitrophenolate-kO] nickel phenyl (triphenyl phosphine), [2,4-diiodo-6-[[[3,3",5,5"-tetrakis(trifluoromethyl)[1,1':3',1"-terphenyl ]-2′-yl]imino-kN]methyl]phenolato-kO]nickel methyl[[3,3′,3″-(phosphinidine-kP)tris[benzenesulfonato]]] trisodium; [2,4-diiodo-6-[[[3,3",5,5"-tetrakis(trifluoromethyl)[1,1':3',1"-terphenyl]-2' -yl]imino-kN]methyl]phenolato-kO]nickel methyl[[3,3'-(phenylphosphiniden-kP)bis[benzenesulfonato]]]-disodium.

suitable for step A) co-catalyst

A co-catalyst may be used if a metal catalyst precursor is applied. The function of this cocatalyst is to activate the metal catalyst precursor. Cocatalysts are for example aluminum alkyls and aluminum alkyl halides such as triethyl aluminum (TEA) or diethyl aluminum chloride (DEAC), MAO, DMAO, MMAO, SMAO (optionally aluminum alkyls such as triiso in combination with butyl aluminum, and/or an aluminum alkyl such as triisobutyl aluminum with a fluorinated aryl borane or a fluorinated aryl borate (i.e., B(R') _y where R' is a fluorinated aryl and y is each 3 or 4) An example of a fluorinated borane is B(C ₆ F ₅ ) ₃ and an example of a fluorination rate is [X] ⁺ [B(C ₆ F ₅ ) ₄ ] ^- (eg X = Ph ₃ C, C ₆ H ₅ N(H)Me ₂ ).

As used herein, methylaluminoxane or MAO may refer to a compound derived from the partial hydrolysis of trimethyl aluminum that serves as a co-catalyst for catalytic olefin polymerization.

Supported methylaluminoxane or SMAO as used herein may refer to methylaluminoxane bound to a solid support.

As used herein, devoid methylaluminoxane or DMAO may refer to methylaluminoxane from which free trimethyl aluminum has been removed.

As used herein, modified methylaluminoxane or MMAO is a modified methylaluminoxane, i.e. obtained after partial hydrolysis of trimethyl aluminum as well as other trialkyl aluminum such as tri(isobutyl) aluminum or tri-n-octyl aluminum. product can mean.

Fluorinated aryl borate or fluorinated aryl borane as used herein shall mean a borate compound having tri- or tetrafluorinated (preferably perfluorinated) aryl ligands, or a borane compound having trifluorinated (preferably perfluorinated) aryl ligands. can

For example, the co-catalyst may be an organometallic compound. The metal of the organometallic compound may be selected from groups 1, 2, 12 or 13 of the IUPAC Periodic Table of Elements. Preferably, the co-catalyst is an organoaluminum compound, more preferably an aluminoxane, which is produced by reacting a trialkyl aluminum compound with water to partially hydrolyze the aluminoxane. For example, trimethyl aluminum can be reacted with water (partial hydrolysis) to form methylaluminoxane (MAO). MAO has the formula (Al(CH ₃ ) _3-n O _0.5n ) _x (AlMe ₃ ) _y having an aluminum oxide structure with a methyl group on an aluminum atom.

MAO generally contains a significant amount of free trimethyl aluminum (TMA), which can be removed by drying the MAO to provide so-called deficient MAO or DMAO. Supported MAO (SMAO) can also be used and can be produced by treatment of an inorganic support material, typically silica, with MAO.

Alternatively, to dry the MAO, if the purpose is to remove free trimethyl aluminum, a bulky phenol reacting with free trimethyl aluminum, such as butylhydroxytoluene (BHT, 2,6-di-t-butyl-4 -methylphenol) may be added.

Neutral Lewis acid modified polymeric or oligomeric aluminoxanes, such as C1-30 hydrocarbyl substituted Group 13 compounds, especially tri(hydrocarbyl) aluminum- or Alkylaluminoxanes modified by addition of tri(hydrocarbyl) boron compounds, or halogenated (including perhalogenated) derivatives thereof, more particularly trialkyl aluminum compounds, may also be used.

Another example of a polymeric or oligomeric aluminoxane is tri(isobutyl) aluminum- or tri(n-octyl) aluminum-modified methylaluminoxane or MMAO, commonly referred to as modified methylaluminoxane. In the present invention, MAO, DMAO, SMAO and MMAO can all be used as co-catalysts.

Additionally, in certain embodiments, metal catalyst precursors are also described in TJ Marks et al., Chem. Rev. 2000, (100), 1391], can be catalytically activated by a combination of an alkylating agent and a cation former which together form a co-catalyst, or, if the catalyst precursor is already alkylated, with the cation former alone. there is. A suitable alkylating agent is a trialkyl aluminum compound, preferably TIBA. Suitable cation formers for use herein are (i) neutral Lewis acids, such as C1-30 hydrocarbyl substituted Group 13 compounds, preferably tris having 1 to 10 carbons in each hydrocarbyl or halogenated hydrocarbyl group. (hydrocarbyl)boron compounds and halogenated (including perhalogenated) derivatives thereof, more preferably perfluorinated tri(aryl)boron compounds, and most preferably tris(pentafluorophenyl)borane, (ii) [C] ⁺ [A] ^- a non-polymerizable, compatible, non-coordinating ion-forming compound of the type (where "C" is a cationic group such as an ammonium, phosphonium, oxonium, silylium or sulfonium group, and [A ^- ] is an anion, in particular, for example borate).

Non-limiting examples of anionic ["A"] are borate compounds, such as C1-30 hydrocarbyl substituted borate compounds, preferably tetra (hydrocarbyl) having 1 to 10 carbons in each hydrocarbyl or halogenated hydrocarbyl group. carbyl)boron compounds and their halogenated (including perhalogenated) derivatives, more preferably perfluorinated tetra(aryl)boron compounds, and most preferably tetrakis(pentafluorophenyl) borate.

Supported catalysts can also be used, for example using SMAO as a co-catalyst. The support material may be an inorganic material. Suitable supports include solid and particulate high surface area metal oxides, metalloid oxides, or mixtures thereof. Examples include talc, silica, alumina, magnesia, titania, zirconia, tin oxide, aluminosilicates, borosilicates, clays, and mixtures thereof.

The preparation of the supported catalyst can be performed using methods known in the art, for example, i) preparing a supported catalyst by reacting a metal catalyst precursor with a supported MAO; ii) reacting the MAO with a metal catalyst precursor and adding the resulting mixture to silica to form a supported catalyst; iii) The metal catalyst precursor immobilized on the support can be reacted with the soluble MAO.

suitable for step A) scavenger

A scavenger may optionally be added to the catalyst system to react with impurities present in the polymerization reactor, and/or solvent and/or monomer feed. This scavenger prevents poisoning of the catalyst during the olefin polymerization process. The scavenger can be the same as the cocatalyst, but also independently aluminum hydrocarbyl (eg triisobutyl aluminum, trioctyl aluminum, trimethyl aluminum, MAO, MMAO, SMAO), zinc hydrocarbyl (eg diethyl zinc) or magnesium hydrocarbyl (eg dibutyl magnesium).

polymerization of olefins

Step A) is the polymerization of at least two olefins to give a copolymerized polyolefin backbone, which step is preferably carried out in an inert atmosphere.

In the present invention, the heteroatom-containing functional group on the second type of olefin monomer is protected or adjusted in situ by a coordinating metal.

The polymerization of olefins can be carried out in the gas phase, for example below the melting point of the polymer. Polymerization can also be carried out in the slurry phase below the melting point of the polymer. Polymerization can also be carried out in solution at a temperature above the melting point of the polymer product.

one or more olefins, such as ethylene or propylene, in the presence of a catalyst based on a transition metal compound belonging to groups 3 to 10 of the Periodic Table of the Elements, for example in a continuous (multi) CSTR or (multi) loop reactor, as a solution or slurry, fluidized or mechanically It is known to polymerize continuously in the gas phase in a reactor with a stirred bed or in a combination of these different reactors.

In gas phase processes, the polymer particles are kept fluidized and/or agitated in a gaseous reaction mixture containing the olefin(s). The catalyst is continuously or intermittently introduced into the reactor while the polymer comprising the fluidized or mechanically stirred bed is continuously or intermittently withdrawn from the reactor. The heat of the polymerization reaction is substantially removed by the gaseous reaction mixture passing through a heat transfer means before being recycled back to the reactor. Additionally, a liquid flow may be introduced into the gas phase reactor to enhance heat removal.

Slurry phase polymerization of olefins is well known, characterized in that olefin monomers and optionally olefin comonomers are polymerized in the presence of a catalyst in a diluent which suspends and conveys the solid polymer product. In such polymerizations, two or more reactors are typically used when a multimodal product is desired, wherein the polymer produced in the first reactor is transferred to a second reactor, where a second polymer having different properties from the first polymer is produced. prepared in the presence of the first polymer. However, it is also possible to connect two reactors producing singlemode polymers to create a swing monomode/multimode plant, or to increase the flexibility of two small reactors that individually may not be economically viable at that scale. It may be desirable to A slurry reactor may also be combined with a gas phase reactor.

Slurry phase polymerization is typically carried out at pressures in the range of 1 to 40 bar and temperatures in the range of 50 to 125 °C. The catalyst used may be any catalyst typically used for olefin polymerizations such as those according to the present invention. The product slurry comprising the polymer and diluent and in most cases also the components of the catalyst system, the olefin monomers and comonomers, is optionally subjected to a thickening device such as a setting leg or hydrocyclone to minimize the amount of fluid discharged with the polymer. may be used intermittently or continuously from each reactor.

Additionally, the present invention can be carried out in a solution polymerization process. Typically, in a solution process, monomers and polymers are dissolved in an inert solvent.

Solution polymerization has several advantages over slurry processes. Because polymerization occurs in a homogeneous phase using a homogeneous single-site catalyst (ie, a metal catalyst or metal catalyst precursor consisting of only one catalytically active site), molecular weight distribution and process parameters are easier to control. High polymerization temperatures, typically above 150° C., also lead to high reaction rates. Solution processes are primarily used for the production of relatively low molecular weight and/or low density resins that are difficult to manufacture by liquid slurry or gas phase processes. Solution processes are well suited for the production of low-density products [Choi and Ray, JMS Review Macromolecular Chemical Physics C25(l), 1-55, pg. 10 (1985), it is considered unsuitable for high molecular weight resins because of their excessive viscosity in the reactor.

Unlike gas phase or slurry processes, polymer solids or powders are usually not formed in solution processes. Typically, reaction temperatures and reaction pressures are higher in gas phase or slurry processes to keep the polymer in solution. Solution processes tend to use an inert solvent that dissolves the polymer that forms, which is then separated and the polymer pelletized. The solution process is considered versatile in that a broad spectrum of product properties can be obtained by varying the composition of the catalyst system, pressure, temperature and monomers used.

Because relatively small reactors are used for the solution process, residence times are short and grade changeovers can be rapid. For example, a series of two reactors operating at a temperature of 250° C. or lower and a pressure of 50 bar or lower in the reactor may be used. The fresh olefin monomer and recycled olefin monomer are compressed to below 55 bar and pumped to the polymerization reactor by a feed pump. The reaction is adiabatic, and the reactor outlet is maintained at a maximum of about 250 °C. Although one reactor may be used, multiple reactors provide a narrow distribution of residence times and thus control of the molecular weight distribution is easier.

In one embodiment of the present invention, the product obtained after step A) may be pre-mixed with the catalyst to be used in step B) prior to step B).

Step B) Polymer chain formation

As mentioned above, during step B) the graft copolymer is formed. Step B) is therefore the formation of polymer side chains on functional short chain branches coordinated with one or more metals to obtain a graft copolymer. That is, step B) is a polymer side chain, i.e. a polymer branch, i.e. It relates to the formation of graft copolymers. This can be done by ROP, for example. This can also be done by a nucleophilic substitution reaction with a pre-synthesized polymer containing a carbonyl group-containing functional group (such as a carboxylic acid or carbonic acid ester functional group). Thus the polymer branches may also be random or block copolymers.

If polar polymer side chains are introduced during step B), their polarity is attached to the polyolefin backbone, for example by adding a plurality of cyclic monomer combinations of different polarity during step B), or via ROP and/or nucleophilic substitution. pre-synthesized homopolymers or copolymers with adjusted polarity that can be used, or a combination of at least two different cyclic monomers or multiple polymers of different polarities are added during step B), or during step B) and by adding a combination of at least one cyclic monomer and at least one polymer capable of being attached to the polyolefin backbone through nucleophilic substitution.

Alternatively, the polarity of the polymer side chains can be adjusted by reacting the polyolefin having metal-adjusted side groups obtained in step A) with a combination of a pre-synthesized polymer for the side chains and a cyclic monomer. Both physical and mechanical properties can be controlled using the process according to the present invention. In addition, hydrolysis and deterioration of polar polymer side chains can be controlled without affecting the polyolefin main chain.

If polyethylene-like polyester side chains are introduced during step B), the obtained copolymer can be used as a compatibilizer for polyolefin-PE blends, in particular iPP-PE blends.

In the case of grafting to the accessible object in step B), the polymer added for grafting onto the main chain contains a carbonyl group-containing functional group, for example a carboxylic acid or carbonic acid ester functional group. Where possible, the polymer side chains are random copolymers or block copolymers.

In this way, a number of polymer blocks or chains are “linked” to the polyolefin backbone containing reactive functional groups. In one embodiment, all polymer side chains are made from the same monomer(s), but may have different average molecular weights. By controlling the reactivity and amount of polymer branches, the properties of the obtained graft copolymer can be easily controlled. In one embodiment, the polymeric side chain is a homopolymer, preferably a polar polymer such as a polyester. Polymer side chains can also be random copolymers or block copolymers. The side chains may all be the same or may be different.

In certain embodiments, the process according to the present invention copolymerizes an olefin, such as ethylene, with a functional (preferably hydroxyl functional) olefin tuned with a metal as comonomer, such as a functional (preferably hydroxyl functional) olefin tuned with a metal, in the next step It consists of two successive steps initiating ROP with the addition of a cyclic monomer, such as a lactone. An advantage of the process of the present invention is that no additional catalyst is required to catalyze the ROP, since the initiator is a catalytic initiator that functions as both an initiator and a catalyst. The product of the first step (step A) is a polyolefin with metal-adjusted side groups. Each of these metal-adjusted side groups can act as ROP initiator and catalyst in step B) to give the graft copolymer.

In a specific embodiment, the process according to the present invention copolymerizes an olefin, such as ethylene, as a comonomer with a functional (preferably hydroxyl functional) olefin tuned with a metal, such as a functional (preferably hydroxyl functional) olefin tuned with aluminum in a first step; , consisting of two successive steps in which, in a subsequent step, a polymer containing reactive carbonyl-containing functional groups is attached as a side chain.

An advantage of the process of the present invention is that no additional catalyst is required to carry out ROP or other carbonyl nucleophilic substitution reactions. The product of the first step (step A) is a polyolefin with metal-adjusted side chains. Each of these metal-adjusted side groups can initiate and catalyze ROP, transesterification or other carbonyl nucleophilic substitution reactions in step B) to give graft copolymers. Step B) is preferably carried out in an inert atmosphere.

Thus, in step A), a functionally tuned functional olefin with one or more metals obtained by copolymerizing at least one olefin monomer of a first type and a functional olefin monomer tuned with a metal of a second type using a catalyst system. A polyolefin backbone with short chain branches can be used to initiate and/or catalyze and/or carry out ROP and/or transesterification and/or another carbonyl nucleophilic substitution reaction in step B). It may in particular be possible to tailor and/or obtain copolymers of functional olefin monomers tuned with at least one second type of metal, for example using aluminum-alkyl, and thus at least one second type of metal. The functional olefin monomers tuned to have/comprise aluminum-alkyl.

Ring-opening polymerization reaction to grow polymer branches

Polymer side chains can be formed by ROP of cyclic monomers during step B) of the process of the invention.

Step A) results in the formation of a polyolefin having functional short branched chain branches coordinated with one or more metals. Functional short-chain branches coordinated with these metals can be used to initiate ROP.

Preferably, the cyclic monomer used by the present invention is an oxygen-containing cyclic compound. The mechanism of ROP is well known to those skilled in the art, for example [Hans book of Ring-Opening Polymerization, 209, Eds. P. Dubois, O. Coulembier, J.-M. Raquez, Wiley VCH, ISBN: 9783527319534.

Mixtures of cyclic monomers can also be used to form random polymer side chains for property control. Sequential addition of different cyclic monomers may also be used.

A major advantage of this method is that no additional catalyst needs to be added. The metal-adjusted functional short-chain branch obtained in step A) is the reactive substituent used in step B).

In the prior art, usually prior to preparation of the polyolefin backbone, metal-adjusted reactive side chains are hydrolyzed to OH groups. Usually an aluminum center is added to these OH groups using, for example, triethyl aluminum. This will lead to Al-O-Pol species that will initiate ROP. However, this additional step is not necessary when using the method according to the present invention.

In one embodiment, cyclic monomers for use in ROP are polar monomers. Polar cyclic monomers are preferably lactones, lactides, cyclic oligoesters (such as di-esters, tri-esters, tetra-esters, penta-esters or higher oligoesters), epoxides, aziridines, epoxides and /or combinations of aziridine and CO ₂ , cyclic anhydrides, epoxides and/or combinations of aziridine and cyclic anhydrides, combinations of epoxides and/or aziridine and CO ₂ and cyclic anhydrides, cyclic It is selected from the group consisting of N-carboxy anhydrides, cyclic carbonates, lactams and combinations of one or more thereof.

Lactones are used to make polylactone side chains; Lactide is used to make polylactide side chains; Cyclic oligoesters (such as diesters, triesters, tetraesters or pentaesters) are used to prepare different kinds of polyester side chains; Epoxides are used to prepare polyether side chains using ROP; Combinations of epoxides and C0 ₂ are used to prepare polycarbonate side chains or poly(carbonate-co-ether) side chains; Combinations of epoxides and cyclic anhydrides are used to prepare polyester side chains or polyester-co-ether side chains; Combinations of epoxides, cyclic anhydrides and C0 ₂ are used to prepare poly(carbonate-co-ester) side chains or poly(carbonate-co-ester-co-ether) side chains; N-carboxy anhydrides are used to make polypeptide side chains; Carbonates are used to make polycarbonate or polycarbonate-co-ether side chains.

Other cyclic monomers include sulfur-containing cyclic compounds such as sulfides; nitrogen-containing cyclic compounds such as amines (aziridines), lactams, urethanes, ureas; phosphorus-containing cyclic compounds such as phosphates, phosphonates, phosphites, phosphines and phosphazenes; silicon-containing cyclic compounds such as siloxanes, and silyl ethers.

In one embodiment, the at least one cyclic monomer for use in ROP is a cyclic hydrocarbyl containing a reactive functional group capable of undergoing a nucleophilic substitution reaction at the carbonyl group-containing functional group, such as a macrolactone or macrooligolactone. A monomer selected from the group consisting of, wherein the monomer contains at least 10 consecutive carbon atoms in the ring/cycle.

When the cyclic monomer is a cyclic ester, it may be a cyclic ester having a ring size of 4 to 40 atoms. Preferably, in the case of cyclic oligoesters, atoms constituting the ester functional group or a ring of ester functional groups are carbon atoms other than oxygen.

Lactones are cyclic compounds with one ester group; Dilactones are compounds with two ester groups; Trilactone is a compound with three ester groups; Tetralactone is a compound with four ester groups; Pentalactone is a compound with 5 ester groups; Oligolactones are compounds having 2 to 20 ester groups.

Examples of cyclic esters which can be used as monomers in step B) are β-propiolactone, β-butyrolactone, 3-methyloxetan-2-one, γ-valerolactone, ε-caprolactone, ε- Decalactone, 5,5-dimethyl-dihydrofuran-2-one, 1,4-dioxepan-5-one, 1,5-dioxepan-2-one, 3,6-dimethylmorpholine-2,5 -Dione, 1,4-dioxepan-7-one, 4-methyl-1,4-dioxepan-7-one, (S)-γ-hydroxymethyl-γ-butyrolactone, γ-octane lactone, γ-nonane lactone, δ-valerolactone, δ-hexalactone, δ-decalactone, δ-undecalactone, δ-dodecalactone, glycolide, lactide (L, D, meso), heptalactone, Octalactone, nonalactone, decalactone, 11-undecalactone, 12-dodecalactone, 13-tridecalactone, 14-tetradecalactone, 15-pentadecalactone (or ω-pentadecalactone), global Lead, 16-hexadecalactone, ambrettolide, 17-heptadecalactone, 18-octadecalactone, 19-nonadecalactone, ethylene brasylate, butylene brasylate, cyclic butyl terephthalate, cyclic butyl adipate, cyclic butyl succinate, and cyclic butyl terephthalate oligomers.

Cyclic esters, especially when they are lactones, may exist in any isomeric form and may additionally contain organic substituents on the ring which do not interfere with the ROP. Examples of such cyclic esters are 4-methyl caprolactone, ε-decalactone, lactones of ricinoleic acid (10-membered ring with hexyl branched on the (co-1)-position) or hydrogenated variants thereof, 13-hexyloxy tetracyclotridecan-2-one (a macrocycle having a hexyl branch on the α-position); and the like. Those lactones having at least 10 methylene units in the ring are considered non-polar monomers in the context of the present invention.

It is further possible that the cyclic ester contains one or more unsaturations in the ring. Examples of such cyclic esters are 5-tetradecene-14-olide, 11-pentadecene-15-olide, 12-pentadecene-15-olide (also called globalide), 7-hexadecene-16-olide. olide (also called ambrettolide) and 9-hexadecene-16-olide.

Cyclic esters may additionally have one or more heteroatoms in the ring, provided they do not interfere with the ROP. Examples of such cyclic esters are 1,4-dioxepan-5-one, 1,5-dioxepan-2-one, 3,6-dimethylmorpholine-2,5-dione, 1,4-oxazepan- 7-one, 4-methyl-1,4-oxazepan-7-one, 10-oxahexadecanolide, 11-oxahexadecanolide, 12-oxahexadecanolide and 12-oxahexadecane-16 -Includes olides.

In one embodiment, a first non-polar monomer is used to form a first polyethylene-like block in the polymer side chain and then a polar monomer is used to form a further block on the non-polar block in the polymer side chain. That is, the side chain itself is a block copolymer.

In one embodiment, the polyolefin is isotactic PP, the non-polar polymer is polyambretolide or polypentadecalactone, and the polar polymer is polycaprolactone or polylactide.

polymer side chain Nucleophilic substitution for addition

During step B) a nucleophilic substitution reaction may be carried out to add polymer side chains to the polyolefin backbone.

Step A) results in the formation of a polyolefin having functional short branched chain branches coordinated with one or more metals. These metal-tailored functional short-chain branches can then be used to carry out nucleophilic substitution reactions.

In the context of the present invention, the nucleophilic substitution reaction is directed to the carbonyl group-containing functional groups present in the polymer added during step B) to the polyolefin having functional short-chain branching coordinated with one or more metals obtained in step A). Describe the nucleophilic reaction with

Combination of ROP and Nucleophilic Substitution for Addition of Polymer Side Chains

Polymer side chains may be formed during step B) of the process of the invention by combining ROP of a cyclic monomer, for example a lactone, with a nucleophilic substitution, for example transesterification.

The polymers having at least one carbonyl group-containing functional group added during step B) to give the graft copolymers are, for example, polyesters, polycarbonates, polyamides, polyurethanes, polyureas, random or block poly(carbonate- ester), poly(carbonate-ether), poly(ester-ether), poly(carbonate-ether-ester), poly(ester-amide), poly(ester-ether-amide), poly(carbonate-amide), poly (carbonate-ether-amide), poly(ester-urethane), poly(ester-ether-urethane), poly(carbonate-urethane), poly(carbonate-ether-urethane), poly(ester-urea), poly(ester -ether-urea), poly(carbonate-urea), poly(carbonate-ether-urea), poly(ether-amide), poly(amide-urethane), poly(amide-urea), poly(urethane-urea) or It may be selected from the group consisting of one or more combinations thereof.

In one embodiment, in addition to the pre-synthesized polymer for the side chain, a cyclic monomer may also be added, for example, with the ROP for the production of the final “polyolefin-g-polar polymer” or “polyolefin-g-polyethylene-like polymer” graft copolymer. are added to provide combinations of nucleophilic substitutions. This approach provides a variety of utilization methods for controlling the physical and mechanical properties of graft copolymers.

In one embodiment, for nucleophilic substitution, a co-catalyst is present during step B). More preferably, when a Cr- or Co-based catalyst is used, an epoxide and/or aziridine is used in combination with CO ₂ or an epoxide and/or aziridine is used in combination with a cyclic anhydride; or epoxides and/or aziridines in combination with C0 ₂ and cyclic anhydrides. Examples of suitable cocatalysts for use include N-methyl-imidazole, 4-dimethylaminopyridine, bis(triphenylphosphoranylidene)ammonium chloride) bis(triphenyl-phosphoranylidene)ammonium azide), tri cyclohexylphosphine, triphenylphosphine, tris(2,4,6-trimethoxyphenyl)phosphine and 1,5,7-triazabicyclododecene.

The main advantage of this process is that no additional catalyst needs to be added in step B), since the metal-adjusted functional short-chain branch obtained in step A) is the reactive substituent used in step B). However, it is possible to add additional catalysts for ROP, transesterification or nucleophilic substitution reactions. Among specific examples of catalysts, inorganic acids, organic acids, organic bases, metal compounds such as hydrocarbyl, oxides, chlorides, carboxylates, alkoxides, aryloxides, amides, salen complexes, β-ketiminato complexes, tin, titanium , guanidineto complexes of zirconium, aluminum, bismuth, antimony, magnesium, calcium and zinc, and lipase enzymes. Examples of suitable catalysts are described in J. Otera and J. Nishikido, Esterification, p. 52-99, Wiley 2010; J. Otera Chem . Rev. 1993, 93 , 1449; H. Kricheldorf Chem . Rev. 2009, 109 , 5579; D. -W. Lee, Y. -M. Park, K.-Y. Lee Catal . Surv . Asia 2009, 13 , 63; AB Ferreira, AL Cardoso, MJ da Silva International Schilarity Research Network , 2012, doi: 10.5402/2012/142857; Z. Helwani, MR Othman, \N. Aziz, J. Kim, WJN Fernando Appl . Catal . A: Gen. 2009, 363 , 1; NE Kamber, W. Jeong, RM Waymouth, RC Pratt, BGG Lohmeijer, JL Hedrick, Chem . Rev., 2007, 107 , 5813; D. Bourissou, S. Moebs-Sanchez, B. Martin-Vaca, CR Chimie , 2007, 10 , as reported in 775].

Examples of organic acids as catalysts for ROP or nucleophilic substitution according to the present invention include diethyl ether complex of hydrogen chloride, fluorosulfonic acid, trifluoromethanesulfonic acid, methyl trifluorosulfonate, ethyl trifluoromethanesulfonate , n-propyl trifluorosulfonate and i-propyl trifluorosulfonate, acids selected from the group comprising metal (yttrium, aluminum and bismuth) triflates; acidic catalysts may also be strong Lewis acids and It may be selected from the group of compounds formed by combining strong Bronsted acids. A specific example of such a compound is an equimolar combination of fluorosulfonic acid and antimony pentafluoride.

Examples of organic bases as catalysts for ROP or nucleophilic substitution according to the present invention are: A base herein is defined as a super base and refers to a compound that exhibits a significantly higher basicity than that of commonly used amines such as pyridine or triethylamine. Superbases can be broadly classified into three categories: organic, organometallic and inorganic. Organic superbases include molecules characterized as amidines, guanidines, multicyclic polyamines and phosphazenes.

Amidines are classified as amine compounds having an imine function adjacent to the α-carbon:

Structurally they correspond to the amine equivalents of carboxylic acid esters. Alkyl substituents R ⁵¹ -R ⁵⁴ are independently selected from hydrogen and C1-C16 alkyl substituents which may be linear, branched, cyclic or aromatic. In addition, these alkyl substituents R ⁵¹ -R ⁵⁴ may be unsaturated, halogenated, or may have specific functional groups such as hydroxyl, ether, amine, cyano or nitro functional groups. Alkyl substituents R ⁵¹ -R ⁵⁴ can also form acyclic structures, where increased ring constraints can lead to stronger basicity. Examples of cyclic amidines are 1,5-diazabicyclo[4.3.0]non-5-ene, 3,3,6,9,9-pentamethyl-2,10-diazabicyclo-[4.4.0 ]dec-1-ene, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). DBU is considered to be the strongest amidine derivative.

Guanidines can likewise be classified as amines with two imine functions adjacent to the α-carbon:

They correspond to the amine equivalents of the ortho esters and exhibit the strongest Bronsted basicity among the amine derivatives. The basicity of guanidine is close to that of the hydroxyl ion, the most powerful base in aqueous chemistry. Alkyl substituents R ⁵⁵ -R ⁵⁹ are independently selected from hydrogen and C1-C16 alkyl substituents which may be linear, branched, cyclic or aromatic. In addition, these alkyl substituents R ⁵⁵ -R ⁵⁹ may be unsaturated, halogenated or may have specific functional groups such as hydroxyl, ether, amine, cyano or nitro functional groups. Alkyl substituents R ⁵⁵ -R ⁵⁹ can also form acyclic structures, where increased ring constraints can lead to stronger basicity. Examples of common guanidines are 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), N-methyl-1,5,7-triazabicyclo[4.4.0]dec-5- N,N,N',N'-tetramethyl-guanidine (TMG) or N,N,N',N',N"-pentamethylguanidine (PMG) may be mentioned.

Phosphazene is an organic super base containing pentavalent phosphorus atoms bonded to four nitrogen functional groups consisting of three amine substituents and one imine substituent.

Phosphazenes are classified as P _n bases, where n represents the number of phosphorus atoms in the molecule. The basicity of phosphazene increases as the amount of phosphorus atoms in the molecule increases. P ₄ bases are thought to have similar basicities to organolithium compounds. Alkyl substituents R ⁶⁰ -R ⁶¹ are independently selected from C1-C16 alkyl substituents which may be linear, branched, cyclic or aromatic. Additionally, these alkyl substituents may be unsaturated, halogenated, or may have specific functional groups such as hydroxyl, ether, amine, cyano or nitro functionalities. Alkyl substituents R can be the same or a mixture of different combinations. A suitable example of the phosphazene according to the present invention is 1-t-butyl-2,2,4,4,4-pentakis(dimethylamino)-2A ⁵ ,4A ⁵ -catenadi(phosphazene) (P ₂ -t -Bu) and 1-t-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)-phosphoranylideneamino]-2A ⁵ ,4A ⁵ -catenadi( phosphazene) (P ₄ -t-Bu).

Examples of organometallic or inorganic bases as catalysts for ROP or nucleophilic substitution according to the present invention are: Organometallic or inorganic superbases consist of metal alkyls, metal alkoxides and metal amides, examples being butyl lithium, potassium t-butoxide, lithium diisopropylamide and lithium bis(trimethylsilyl)amide. A mixture of organometallic super bases can also be used to further enhance the reactivity. A mixture of butyl lithium and potassium t-butoxide is one example. Inorganic super bases are compounds with anions that are usually small in size and exhibit high charge densities, such as metal hydrides and lithium nitride in general are given as examples.

Examples of tin-based catalysts for ROP or nucleophilic substitution according to the present invention are as follows. Tetravalent tin compounds used as metal catalysts include tin oxide, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin di(2-ethylhexoate), dibutyltin dilaurate, and dibutyltin maleate. , di(n-octyl)tin maleate, bis(dibutyl acetoxy tin)oxide, bis(dibutyl lauryloxytin)oxide, dibutyltin dibutoxide, dibutyltin dimethoxide, dibutyl Tin Disalicylate, Dibutyltin Bis(isooctyl Maleate), Dibutyltin Bis(Isopropyl Maleate), Dibutyltin Oxide, Tributyltin Acetate, Tributyltin Isopropyl Succinate, Tributyltin Linoleate, tributyltin nicotinate, dimethyltin dilaurate, dimethyltin oxide, dioctyltin oxide, bis(tributyltin)oxide, diphenyltin oxide, triphenyltin acetate, tripropyl tin acetate, tripropyltin laurate and bis(tripropyltin)oxy. Suitable tin-containing compounds include divalent stannous carboxylate groups derived from monobasic acids, aliphatic dibasic acids, aliphatic tribasic acids, aromatic monobasic acids, aromatic dibasic acids or aromatic tribasic acids, as described below in connection with the preparation of the esters. It includes the carboxylate salt of The carboxylate salt can be added as such or it can be formed 'in situ' by reacting divalent tin oxide with a carboxylic acid. As the divalent tin oxide, tin oxide, bis(2-ethylhexanoate), tin bis(2,6-tBu-4-Me-C ₆ H ₂ O), tin oxalate, and tin dichloride are used.

Examples of titanium-based catalysts for ROP or nucleophilic substitution according to the present invention are as follows. Titanium compounds that can be used include tetramethyl titanate, tetraethyl titanate, tetraallyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetraisobutyl titanate, tetraamyl titanate, tetraamyl titanate, and tetrabutyl titanate. Cyclopentyl titanate, tetrahexyl titanate, tetracyclohexyl titanate, tetrabenzyl titanate, tetraoctyl titanate, tetra(2-ethyl-hexyl) titanate, tetranonyl titanate, tetradecyl titanate, and tetraole yl titanate, tetraphenyl titanate, tetra(o-tolyl) titanate and tetra(m-tolyl) titanate, and tetra(1-naphthyl) titanate and tetra(2-naphthyl) titanate. there is. Examples of mixed alkyl titanate compounds include trimethylbutyl titanate, dimethyldibutyl titanate, triethylbutyl titanate, methyl isopropyl dibutyl titanate, diethyl dibutyl titanate, propyl tributyl titanate, and ethyl tricyclohexyl titanate. , diisopropyl dioctadecyl titanate, and dibutyl dioctadecyl titanate.

Examples of bismuth-based catalysts for ROP, transesterification or nucleophilic substitution according to the present invention are: bismuth tris(2-ethyl-hexanoate), bismuth trisacetate, bismuth trishexanoate, bismuth tristri Plate, bismuth subsalicylate (also called orthosalicylate), bismuth subcarbonate, BiCl ₃ , BiBr ₃ , BiI ₃ , Bi ₂ O ₃ , Ph ₂ BiOEt, Ph ₂ BiOMe, Ph ₂ BiOtBu, Ph ₂ BiOBr, Ph ₂ BiI, [SCH ₂ CH ₂ O]Bi[SCH ₂ CH ₂ OH], B(OEt) ₃ , bismuth aminotriethanolate, bismuth lactate, bismuth nitrate, bismuthyl nitrate, bismuth carbonate, bismuthyl carbonate , bismuthyl hydroxide, bismuth orthohydroxide (Bi(OH) ₃ ).

Examples of organometallic/metal coordination complexes for use as catalysts for ROP, transesterification or nucleophilic substitution according to the present invention are: Li, Na, K, Mg, Ca, Sc, Y, lanthanides, metal halides of Ti, Zr, Zn, Al, Ga, Bi and Sn, triflates, hydrocarbyls, alkoxides, aryloxides, amides, carboxyl In addition to complexes consisting of rates, acetylacetonate complexes, or combinations of these substituents, well-defined and well-defined organometallic and metal coordination complexes containing various cyclic esters or ROPs of cyclic carbonates, and carboxylic acid esters or carbonic acid esters. It is applied as a metal catalyst for transesterification of polymers. Examples include Mg, Ca, Sc, Y, lanthanide, Ti, Zr, Zn, Al, Ga, Bi and Sn of salen, salan, salalen, guanidinate, porphyrin, β-ketiminate, phenoxy-imine , phenoxy-amines, bisphenolates, trisphenolates, alkoxyamines, alkoxyethers and alkoxythioether complexes.

Recently, for example [O'Keefe et al. (BJ O'Keefe, MA Hillmyer, WB Tolman, J. Chem . Soc ., Dalton Trans., 2001, 2215-2224)], or [Lou et al. (Lou, C. Detrembleur, R. Jerome, Macromol . Rapid. Commun ., 2003, 24, 161-172)], or [Nakano et al. (K. Nakano, N. Kosaka, T. Hiyama, K. Nozaki, J. Chem . Soc ., Dalton Trans., 2003, 4039-4050)], or [Dechy-Cabaret et al. (O. Dechy-Cabaret, B. Martin-Vaca, D. Bourissou, Chem . Rev., 2004, 104, 6147-6176)], or [Wu et al. (Wu, T.-L Yu, C.-T. Chen, C.-C. Lin, Coord . Chem . Rev., 2006, 250, 602-626)], or [Amgoune et al. (Amgoune, CM Thomas, J.-F. Carpentier, Pure Appl. Chem . 2007, 79, 2013-2030), various isomers of LA, namely rac- , L-, D- and meso-LA A number of well-defined metal initiators have been developed for the controlled production of ROP. These are mainly nontoxic zinc (M. Cheng, AB Attygalle, EB Lobkovsky, GW Coates, J. Am. Chem . Soc ., 1999, 121, 11583-11584; BM Chamberlain, M. Cheng, DR Moore, TM Ovitt, EB Lobkovsky, GW Coates, J. Am. Chem . Soc ., 2001, 123, 3229-3238; Chem . _ _ _ _ Fablet, M. Bouyahyi, CM Thomas, T. Roisnel, O. Casagrande Jr., J.-F. Carpentier, New J. Chem ., 2008, 32, 2279-2291), aluminum (N. Spassky, M. Wisniewski , C. Pluta, A. LeBorgne , Macromol . Chem . Phys., 1996 , 197, 2627-2637 TM Ovitt , GW Coates, J. Am. , GW Coates, J. Am. Chem . Soc ., 2002, 124, 1316-1326 N. Nomura, R. Ishii, Y. Yamamoto, T. Kondo, Chem . Eur . J., 2007, 13, 4433- 4451; H. Zhu, EY-X. Chen, Organometallics, 2007, 26, 5395-5405), non-toxic bismuth (H. Kricheldorf Chem . R ev. 2009, 109 , 5579) or group 3 metals and lanthanides (C.-X. Cai, A. Amgoune, CW Lehmann, J.-F. Carpentier, Chem . Commun ., 2004, 330-331; A. Amgoune, CM Thomas, T. Roisnel, J.-F. Carpentier, Chem. Eur . J., 2006, 12, 169-179; , Angew . Chem . Int. Ed., 2006, 45, 2782-2784).

The amount of additional catalyst used in step B) is selected, for example, from the range of 0.0001 to 0.5% by weight, preferably from 0.001 to 0.1% by weight, based on the number of carbonyl functions or cyclic esters in the polymer added during step B). do.

After completion of step B), a graft copolymer is obtained. In one embodiment, the reaction mixture is quenched using a quenching agent, preferably a protic polar reagent, more preferably an alcohol, preferably methanol or ethanol. But you can also use water. The product obtained after this quenching is a crude product which may also contain polyolefins obtained in step A) and/or polymers not attached to the polyolefin backbone obtained by ROP and/or nucleophilic substitution reactions in step B). However, for most applications the crude product can be used as is without further purification.

If ROP or the polymer obtained from the nucleophilic substitution reaction in step B) is to be removed from the product, this crude product may, for example, be subjected to a further work-up step. This work-up step may include precipitation, for example in a solvent such as THF or another organic solvent such as chloroform. If the polymer for the side chain is polar, the process may also be called extraction, since any polar homopolymer formed will be extracted from the crude product, leaving a graft copolymer of the olefin and possibly a homopolymer.

One skilled in the art will be able to determine the steps required to purify the copolymer product, for example using one or more precipitation and/or extraction steps using one or more solvents. The product may be dried prior to its use.

addition specific example

The present invention relates to a two-step process for the preparation of graft copolymers.

Graft copolymers can be obtained using the method according to the present invention. In one embodiment, the graft copolymer has a number average molecular weight (M _n ) of, for example, 500 to 1,000,000 g/mol, preferably 1,000 to 200,000 g/mol.

The polyolefin-based graft copolymer obtained after step B) of the present invention preferably has a polydispersity index ( Ð ) of from 1.1 to 10.0, more preferably from 1.1 to 5.0, more preferably from 1.1 to 4.0, even more preferably. 1.5 to 3.

The polyolefin backbone can be linear or branched (both branched long chains and branched short chains), isotactic, or syndiotactic, preferably isotactic polyolefins in the case of poly α-olefins, which are preferably It is preferably isotactic polypropylene.

According to certain non-limiting embodiments of the present invention, the polyolefin backbone is linear low density polyethylene (LLDPE), high density polyethylene (HDPE), ethylene-propylene copolymer (EP), atactic, isotactic or syndiotactic PP (each aPP). , iPP, sPP), poly-4-methyl-1-pentene (P4M1P) or atactic, isotactic or syndiotactic polystyrene (aPS, iPS, sPS, respectively).

The mass fraction of polyolefin ( mf Pol) of the graft copolymer according to the present invention may be 10% to 90%, preferably 30% to 70%. The mass fraction mf Pol is defined as the weight of the polyolefin divided by the total mass of the copolymer.

The graft copolymer according to the present invention may have a volume fraction of the polymer relative to the side chain ( vf Pol) of 90% to 10%, preferably 70% to 30%. The volume fraction ( vf Pol) is defined as the volume of polymer for side chains divided by the total volume of the copolymer.

Examples of polymers having a polyolefin backbone and polar polymer side chains that can be prepared using the process of the present invention include HDPE-g-PCL, HDPE-g-PLA, HDPE-g-PBA, HDPE-g-PBS, HDPE-g -PEB, HDPE-g-poly(CL-co-PDL), HDPE-g-poly(BA-co-EB), HDPE-g-poly(BA-co-PDL), LLDPE-g-PCL, LLDPE- g-PLA, LLDPE-g-PBA, LLDPE-g-PBS, LLDPE-g-PEB, LLDPE-g-poly(BA-co-EB), LLDPE-g-poly(CL-co-PDL), LLDPE- g-poly(BA-co-PDL), EP-g-PCL, EP-g-PLA, EP-g-PBA, EP-g-PBS, EP-g-PEB, EP-g-poly(BA-co -EB), EP-g-poly(CL-co-PDL), EP-g-poly(BA-co-PDL), aPP-g-PCL, iPP-g-PLA, aPP-g-PBA, aPP- g-PBS, aPP-g-PEB, aPP-g-poly(BA-co-EB), aPP-g-poly(CL-co-PDL), aPP-g-poly(BA-co-PDL), iPP -g-PCL, iPP-g-PLA, iPP-g-PBA, iPP-g-PBS, iPP-g-PEB, iPP-g-poly(BA-co-EB), iPP-g-poly(CL- co-PDL), iPP-g-poly(BA-co-PDL), sPP-g-PCL, sPP-g-PLA, sPP-g-PBA, sPP-g-PBS, sPP-g-PEB, sPP- g-poly(BA-co-EB), sPP-g-poly(CL-co-PDL), sPP-g-poly(BA-co-PDL), iP4M1P-g-PCL, iP4M1P-g-PBA, iP4M1P -g-PBS, iP4M1P-g-PEB, iP4M1P-g-poly (BA-co-EB), iP4M1P-g-poly (CL-co-PDL), iP4M1P-g-poly (BA-co-PDL), aPS-g-PCL, aPS-g-PBA, aPS-g-PBS, aPS-g-PEB, aPS-g-poly(BA-co-EB), aPS-g-poly(CL-co-PDL), aPS-g-poly(BA- co-PDL), iPS-g-PCL, iPS-g-PBA, iPS-g-PBS, iPS-g-PEB, iPS-g-poly(BA-co-EB), iPS-g-poly(CL- co-PDL), iPS-g-poly(BA-co-PDL), sPS-g-PCL, sPS-g-PBA, sPS-g-PBS, sPS-g-PEBL, sPS-g-poly(BA- co-EB), sPS-g-poly(CL-co-PDL), sPS-g-poly(BA-co-PDL) and many other polymers.

Examples of polymers having a polyolefin backbone and polyethylene-like polymer side chains that can be prepared using the process of the present invention include HDPE-g-PPDL, HDPE-g-PAmb, HDPE-g-poly(PDL-co-Amb), LLDPE -g-PPDL, LLDPE-g-PAmb, LLDPE-g-poly(PDL-co-Amb), EP-g-PPDL, EP-g-PAmb, EP-g-poly(PDL-co-Amb), aPP -g-PPDL, aPP-g-PAmb, aPP-g-poly(PDL-co-Amb), iPP-g-PPDL, iPP-g-PAmb, iPP-g-poly(PDL-co-Amb), sPP -g-PPDL, sPP-g-PAmb, sPP-g-poly(PDL-co-Amb), iP4M1P-g-PPDL, iP4M1P-g-PAmb, iP4M1P-g-poly(PDL-co-Amb), aPS -g-PPDL, aPS-g-PAmb, aPS-g-poly(PDL-co-Amb), iPS-g-PPDL, iPS-g-PAmb, iPS-g-poly(PDL-co-Amb), sPS -g-PPDL, sPS-g-PAmb, sPS-g-poly (PDL-co-Amb).

Examples of polymers having a polyolefin backbone and polyethylene-like and polar side chains that can be prepared using the process of the present invention include HDPE-g-PPDL-g-PCL, HDPE-g-PAmb-g-PCL, HDPE-poly(PDL -co-Amb)-g-PCL, LLDPE-g-PPDL-g-PCL, LLDPE-g-PAmb-g-PCL, LLDPE-Poly(PDL-co-Amb)-g-PCL, EP-g-PPDL -g-PCL, EP-g-PAmb-g-PCL, EP-g-poly(PDL-co-Amb)-g-PCL, aPP-g-PPDL-g-PCL, aPP-g-PAmb-g- PCL, aPP-poly(PDL-co-Amb)-g-PCL, iPP-g-PPDL-g-PCL, iPP-g-PAmb-g-PCL, iPP-poly(PDL-co-Amb)-g- PCL, sPP-g-PPDL-g-PCL, sPP-g-PAmb-g-PCL, sPP-poly(PDL-co-Amb)-g-PCL, iP4M1P-g-PPDL-g-PCL, iP4M1P-g -PAMb-g-PCL, iP4M1P-g-poly(PDL-co-Amb)-g-PCL, aPS-g-PPDL-g-PCL, aPS-g-PAmb-g-PCL, aPS-poly(PDL- co-Amb)-g-PCL, iPS-g-PPDL-g-PCL, iPS-g-PAmb-g-PCL, iPS-poly(PDL-co-Amb)-g-PCL, sPS-g-PPDL- g-PCL, sPS-g-PAmb-g-PCL, and sPS-poly(PDL-co-Amb)-g-PCL.

According to certain non-limiting embodiments of the present invention, the polyolefin backbone may be HDPE, LLDPE, EP, aPP, iPP, sPP, iP4M1P, aPS, iPS or sPS.

Copolymers prepared according to the present invention can be used to enhance interfacial interactions in polyolefin blends with polar polymers or blends of different polyolefins with PE, for example with polar incorporation. They can be used as compatibilizers to improve properties such as adhesion. They can be used to improve the barrier properties to polyolefin films, especially to oxygen. They can be used for polyolefin-based composites with inorganic fillers such as glass or talc, or as compatibilizers for highly polar polymers such as starches. They may also be used in drug delivery devices, non-porous materials/membranes.

Advantages of the Invention

An advantage of the present invention is the reduction in the number of process steps required for the synthesis of the copolymer. The method according to the invention is less time, energy and material consuming than methods according to the prior art.

Another advantage of the present invention is that in principle only one single catalyst is required during the entire process, such as the metal catalyst or metal catalyst precursor in step A). The metals used to protect the functional groups of the functional comonomers in step A) act as initiators and catalysts during step B).

The process according to the invention may be a so-called cascade or cascade-type process. Thus preferably, step B) can be carried out immediately after step A) and step C) can be carried out immediately after step B), preferably in a series of connected reactors, preferably continuously. Thereby, this process according to the invention can be carried out without a metal-replacement step, for example by hydrolysis. The metal-replacement step can be any step that provides a reactive organic functional group, for example by removing a metal. Preferably, steps A), B) and C) are carried out in a so-called cascade-type process. In other words, the process can be a single multi-stage process using a series of reactors without metal-replacement, for example by hydrolysis, without work-up, without drying and/or without purification steps. It should be noted that an extruder is also considered a reactor in the context of the present invention. An extruder is also considered a reactor in the context of the present invention.

The desired graft polymer can be obtained in high yield and thus the number of process steps required in prior art processes such as intermediate work-up, filtration, drying and the like can be significantly reduced. This is an advantage of the present invention.

Example

The invention is further illustrated by the following non-limiting examples, which are used only to further illustrate certain embodiments of the invention.

All manipulations were performed under an inert dry nitrogen atmosphere using standard Schlenk or glove box techniques. Dry oxygen-free toluene was used as all polymerization solvents. rac -Me ₂ Si(Ind) ₂ ZrCl ₂ ( 1 ) and rac - Me ₂ Si (2-Me-4-Ph-Ind) ₂ ZrCl ₂ ( 2 ) were purchased from MCAT GmbH, Constance, Germany. did C ₅ Me ₄ CH ₂ CH ₂ NMe ₂ ]TiCl ₂ ( 3 ) was prepared as described in WO9319104. Methylaluminoxane (MAO, 30% by weight solution in toluene) was purchased from Chemtura. Diethyl zinc (1.0 M solution in hexanes), tri(i-butyl) aluminum (1.0 M solution in hexanes), tetrachloroethane- d ₂ (TCE- d ₂ ) and CL were purchased from Sigma Aldrich. 10-undecen-1-ol (C11OH) was purchased from Aldrich and dried over a 4-Å molecular sieve under an inert atmosphere.

Typical polymerization procedure

For the production of polyethylene-graft-polycaprolactone copolymer, a sequential feeding method carried out in a single batch reactor was applied. The first stage A) consists of ethylene/C11OH copolymerization, followed by the ROP of CL (stage B). The polymerization reaction was carried out in a stainless steel Buchi reactor. Prior to polymerization, the reactor was vacuum dried at 40° C. and flushed with nitrogen. Toluene solvent (70 mL) followed by TIBA and functional monomers were introduced under an inert atmosphere. After the resulting solution was stirred for 15 to 20 minutes, the calculated amount of co-catalyst was added under a nitrogen atmosphere. The polymerization reaction was initiated by adding a metal catalyst precursor to the reactor. The reactor was pressurized with ethylene to the desired pressure and the pressure was held for a period of time. The supply of ethylene was stopped, and the residual pressure was released. Via the liquid injection tube, a calculated amount of CL monomer was added under an inert atmosphere, and the suspension was maintained at 60° C. under rigorous stirring (600 rpm) for a given period of time. The reaction was terminated by precipitation in acidic methanol (10% concentrated hydrochloric acid) and PE-graft-PCL copolymer and PCL material were isolated.

analytical skills

¹ H-NMR analysis was performed at 80 to 110 °C using TCE- d ₂ as solvent and recorded on a Varian Mercury spectrophotometer operating at a frequency of 400 MHz in a 5 mm tube. Chemical shifts are reported in ppm relative to tetramethylsilane and determined with reference to residual solvent.

Heteronuclear multi-bonding correlation spectra (HMBC) were recorded with pulse field gradients. The spectral windows of the 1H and 13C axes were 6075.3 and 21367.4 Hz, respectively. Data were collected in a 2560 × 210 matrix and processed into a 1K × 1K matrix. Spectra were recorded with an acquisition time of 0.211 s, a relaxation delay of 1.4 s and a number of scans in 144 × 210 increments.

Solid-phase ¹³ C{ ¹ H} cross polarization/magic-angle spinning (CP/MAS) NMR and ¹³ C{ ¹ H} INEPT (Insensitive Nuclei Enhanced by polarization transfer) experiments were performed using double-resonance with a rotor of 2.5 mm outer diameter. It was performed on a Bruker AVANCE-III 500 spectrophotometer employing an HX probe. These experiments employed a MAS frequency of 25.0 kHz, 2.5 μs π/2 pulses for ¹ H and ¹³ C NMR, CP contact time of 2.0 ms, and TPPM decoupling during acquisition. CP conditions were previously optimized using L-alanine. ¹³ C{ ¹ H} INEPT spectra were recorded using a refocused-INEPT sequence with a J-evolution period of 1/3 J _CH or 6/1 J _CH (assuming ¹ J _CH of 150 Hz), i.e., For the J-evolution period of 1/3 J _CH the signals from CH and CH ₃ groups are positive and those of CH ₂ are negative. ² D ¹ H- ¹ H Double quantum-single quantum (DQ-SQ) correlation experiments and DQ accumulation experiments were performed on a Bruker AVANCE-III 700 spectrophotometer employing a 2.5 mm solid-state MAS double resonance probe. These experiments used a rotational frequency of 25.0 kHz. DQ excitation and reconversion were performed using a broadband back-to-back (BaBa) sequence. Chemical shifts for the ¹ H and ¹³ C NMR spectra were reported for TMS using solid adamantane as an external standard.

Size Exclusion Chromatography (SEC). Molecular weights ( M _n and M _w ) and Ð in g/mole were determined by high temperature size exclusion chromatography performed at 160° C. using high-speed GPC (Freeslate, Sunnyvale, USA). Detection: IR4 (from PolymerChar, Valescia, Spain). Column setup: 3 Polymer Laboratories 13 μm PLgel Olexis, 300×7.5 mm. As an eluent, 1,2,4-trichlorobenzene (TCB) was used at a flow rate of 1 mL min ^-1 . TCB was freshly distilled before use. Molecular weights and corresponding Ð were calculated from HT SEC analysis against narrow polyethylene standards (PSS, Mainz, Germany). HT SEC of the copolymers was performed at 160 °C on a Polymer Laboratories PLXT-20 rapid GPC polymer analysis system (refractive index detector and viscosity detector) equipped with 3 PLgel Olexis (300 × 7.5 mm, Polymer Laboratories) columns in series. As an eluent, TCB was used at a flow rate of 1 mL·min ^-1 . _Molecular weights ( Mn and Mw ₎ were calculated against polyethylene standards (Polymer Laboratories). A Polymer Laboratories PL XT-220 robotic sample handling system was used as an autosampler.

Differential Scanning Calorimetry (DSC). Melting ( T _m ) and crystallization ( T _c ) temperatures as well as transition enthalpies were measured by DSC using a DSC Q100 from TA Instruments. The measurement was performed at a heating and cooling rate of 10 °C·min ^-1 from -60 °C to 160 °C. Transitions were estimated from the second heating and cooling curves.

Example 1 and 2

Step A) was carried out using ethylene as the first type of olefin monomer, in situ protected C11OH as the second type of olefin monomer and 1 as the metal catalyst precursor. Also, TIBA and MAO were used. During step B), the ROP process was carried out using CL as cyclic monomer.

Example 3 and 4

Step A) was carried out using ethylene as the first type of olefin monomer, in situ protected C11OH as the second type of olefin monomer and 2 as the metal catalyst precursor. Also, TIBA and MAO were used. During step B), the ROP process was carried out using CL as cyclic monomer.

Example 5 and 6

Step A) was carried out using ethylene as the first type of olefin monomer and 3 as the metal catalyst precursor. Also, TIBA and MAO were used. During step B), the ROP process was carried out using CL as cyclic monomer.

Example 7 and 8

Step A) was carried out using ethylene as the first type of olefin monomer, in situ protected C11OH as the second type of olefin monomer and 1 as the metal catalyst precursor. Also, TIBA, MAO and BHT were used. During step B), the ROP process was carried out using CL as cyclic monomer.

Example catalyst ^a MAO ^b molar ratio ^c C2 ^d CL ^e crude
yield ^f in THF
yield ^g
M _n
( Ð ) ^h One 2 3 One 10 -- -- 1000 500/150/1 3.0 (15) 35 (60) 2.6 -- 9,400
(2.3) 2 10 -- -- 1000 500/150/1 3.0 (30) 35 (60) 5.5 -- 10,200 (3.5) 3 -- 10 -- 1000 500/150/1 3.0 (15) 35 (60) 3.2 -- 7,600
(3.3) 4 -- 10 -- 1000 500/150/1 3.0 (30) 35 (60) 5.3 -- 10,300 (3.5) 5 -- -- 10 1000 500/250/1 3.0 (15) 35 (60) 6.1 -- 6,100
(4.3) 6 -- -- 10 1000 500/250/1 3.0 (30) 35 (60) 9.9 -- 8,200
(4.4) 7 10 -- -- 1000 300/150/1 3.0 (35) 35 (60) 10.5 5.2 -- 8 10 -- -- 1000 150/75/1 3.0 (30) 35 (60) 11.6 8.5 --

a) μmol of metal catalyst precursor: rac -Me ₂ Si(Ind) ₂ ZrCl ₂( 1); rac -Me ₂ Si(2-Me-4-Ph-Ind) ₂ ZrCl ₂ ( 2 ); Ti:[C ₅ Me ₄ CH ₂ CH ₂ NMe ₂ ]TiCl ₂ ( 3 );

b) mmol (M) of MAO co-catalyst;

c) the molar ratio of TIBA:C11OH:catalyst; TIBA is used as a chain transfer agent; C11OH is an in situ protected 10-undecen-1-ol used as a comonomer;

d) C2: ethylene pressure in bars and reaction time in minutes in parentheses;

e) Values quoted are quantities in mmol. Values in parentheses are times in minutes;

f) Crude yield is the yield in grams after precipitation in acidified methanol. It may include a mixture of the desired graft copolymer and one or more homopolymers;

g) the yield in THF is the yield after precipitation in THF to remove any PCL homopolymer that is soluble in THF;

h) M _n is the number average molecular weight in g/mol and the value in parentheses is the polydispersity index.

From Table 1, the following can be observed. By using the process according to the present process it is possible to obtain graft copolymers with a number of different types of catalysts in step A).

Example 9

Step A) was carried out using propylene as the first type of olefin monomer, in situ protected C11OH as the second type of olefin monomer and 1 as the metal catalyst precursor. Also, TIBA and MAO were used. During step B), the ROP process was carried out using CL as cyclic monomer.

Example 10

Step A) was carried out using propylene as the first type of olefin monomer, in situ protected C11OH as the second type of olefin monomer and 1 as the metal catalyst precursor. Also, TIBA and trityl tetrakis(pentafluorophenyl)borate were used. During step B), the ROP process was carried out using CL as cyclic monomer.

Example 11

Step A) was carried out using propylene as the first type of olefin monomer, in situ protected C11OH as the second type of olefin monomer and 2 as the metal catalyst precursor. Also, TIBA and MAO were used. During step B), the ROP process was carried out using CL as cyclic monomer.

Example 12

Step A) was carried out using propylene as the first type of olefin monomer, in situ protected C11OH as the second type of olefin monomer and 2 as the metal catalyst precursor. Also, TIBA and trityl tetrakis(pentafluorophenyl)borate were used. During step B), the ROP process was carried out using CL as cyclic monomer.

Example catalyst ^a Borate: Catalyst MAO ^b molar ratio ^{c C3d} CL ^e crude
yield ^f Yield in THF M _n
(Ð) ^g One 2 9 10 -- 0 1000 500/250/1 3.0 (15) 35 (60) 28.2 12.3 10 10 -- 1.5 0 500/250/1 3.0 (30) 35 (60) 7.3 5.6 11 -- 10 0 1000 500/250/1 3.0 (15) 35 (60) 18.3 11.3 12 -- 10 1.5 0 500/250/1 3.0 (15) 35 (60) 6.9 4.3

a) μmol of metal catalyst precursor: rac -Me ₂ Si(Ind) ₂ ZrCl ₂( 1); rac -Me ₂ Si(2-Me-4-Ph-Ind) ₂ ZrCl ₂ ( 2 );

b) mmol (M) of MAO co-catalyst;

c) the molar ratio of TIBA:C11OH:catalyst; TIBA is used as a chain transfer agent; C11OH is an in situ protected 10-undecen-1-ol used as a comonomer;

d) C3: propylene pressure in bars and reaction time in minutes in brackets;

e) Values quoted are quantities in mmol. Values in parentheses are times in minutes;

f) Crude yield is the yield in grams after precipitation in acidified methanol. It may include a mixture of the desired graft copolymer and one or more homopolymers;

g) the yield in THF is the yield after precipitation in THF to remove any PCL homopolymer that is soluble in THF;

h) M _n is the number average molecular weight in g/mol and the value in parentheses is the polydispersity index.

From the above, the following can be observed. Various graft copolymers can be obtained by adjusting the polyolefin main chain and adjusting the monomers used for preparing the polymer side chain using the method according to the method of the present invention. In addition, a number of catalysts can be used to produce side chain branches.

Claims (17)

A) i) a metal catalyst or metal catalyst precursor comprising a metal of Groups 3 to 10 of the IUPAC Periodic Table of Elements; and
ii) optionally a co-catalyst;
One or more metal-pacified functional olefin monomers are copolymerized with at least one first type olefin monomer and at least one second type metal-pacified functional olefin monomer using a catalyst system comprising obtaining a polyolefin main chain having functional short chain branches; and
B) using the metal-adjusted functional short-chain branching on the polyolefin backbone obtained in step A) as a catalytic initiator to obtain a graft copolymer to form one or a plurality of polymer side chains on the polyolefin backbone.
including,
Step B) for obtaining the graft copolymer is carried out by a nucleophilic substitution reaction at the carbonyl group-containing functional group of at least one kind of polymer for the side chain, or
In step B) for obtaining the graft copolymer, ring opening polymerization (ROP) using at least one kind of cyclic monomer and nucleophilicity at the carbonyl group-containing functional group of at least one kind of polymer for the side chain carried out by a combination of substitution reactions,
A process for preparing a graft copolymer comprising a polyolefin backbone and one or a plurality of polymer side chains. The method of claim 1 , wherein the method is a single process using a series of reactors. delete delete delete 2. The method of claim 1, wherein said at least one olefin monomer of the first class is a compound according to Formula IA:
[Formula IA]

In the above formula,
C is carbon;
R ^1a , R ^1b , R ^1c , and R ^1d are each independently selected from the group consisting of H or hydrocarbyl of 1 to 16 carbon atoms; or,
wherein the at least one first type of olefin monomer is selected from the group consisting of 1-cyclopentene, cyclohexene, norbornene, ethylidene-norbornene, vinylidene-norbornene, and combinations of one or more thereof; method. The method of claim 1 , wherein the functional olefin monomer adjusted with at least one second type of metal is a compound according to formula (IB):
[Formula IB]

In the above formula,
C is carbon;
R ² , R ³ , and R ⁴ are each independently selected from the group consisting of H or hydrocarbyl of 1 to 16 carbon atoms;
R ⁵ -X-ML _n is a heteroatom-containing functional group coordinated with a main group metal, wherein X is a heteroatom or heteroatom-containing group, and the heteroatom bonded to M is from the group consisting of O, S and N selected; R ⁵ is hydrocarbylene of 1 to 16 carbon atoms, wherein M is a main group metal, L is a ligand, n is 0, 1, 2 or 3 and the total charge of L _n is 1 in the oxidation state of the main group metal corresponds to minus The process according to claim 1 , wherein during step B) no additional catalyst for the ring opening polymerization (ROP) or the nucleophilic substitution reaction is added. The method of claim 1, wherein the metal catalyst or metal catalyst precursor used in step A) comprises a metal of Groups 3 to 8 of the IUPAC Periodic Table of Elements and/or the metal catalyst or metal catalyst precursor used in step A) is Ti , Zr, Hf, V, Cr, Fe, Co, Ni, and a method comprising a metal selected from the group consisting of Pd. The method of claim 1, wherein the cocatalyst is used in the catalyst system, and the cocatalyst is selected from methylaluminoxane (MAO), depleted methylaluminoxane (DMAO), modified methylaluminoxane (MMAO), supported methylaluminoxane (SMAO), fluorinated aryl borane or fluorinated aryl borate. Which is selected from the group consisting of, method. 7. The method of claim 6, wherein the olefin monomer according to Formula I-A is ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, and combinations of one or more of these Which is selected from the group consisting of, method. According to claim 1,
wherein said cyclic monomers used during said ring-opening polymerization (ROP) in step B) are selected from the group consisting of lactones, lactides, cyclic oligoesters, epoxides, aziridines, one or both of epoxides and aziridines, and a combination of CO ₂ , a cyclic anhydride, a combination of one or both of an epoxide and an aziridine with a cyclic anhydride, a combination of one or both of an epoxide and an aziridine with CO ₂ and a cyclic anhydride, a cyclic N-carboxy anhydride , a polar monomer selected from the group consisting of cyclic carbonates, lactams, and combinations of one or more thereof;
wherein the cyclic monomer used during the ring-opening polymerization (ROP) in step B) is a non-polar cyclic monomer having a ring size of at least 12 atoms. The method of claim 1, wherein at least one kind of polymer for said side chain added during step B) is polyester, polycarbonate, polyamide, polyurethane, polyurea, random or block poly(carbonate-ester), poly(carbonate -ether), poly(ester-ether), poly(carbonate-ether-ester), poly(ester-amide), poly(ester-ether-amide), poly(carbonate-amide), poly(carbonate-ether-amide) ), poly(ester-urethane), poly(ester-ether-urethane), poly(carbonate-urethane), poly(carbonate-ether-urethane), poly(ester-urea), poly(ester-ether-urea), Poly(carbonate-urea), poly(carbonate-ether-urea), poly(ether-amide), poly(amide-urethane), poly(amide-urea), poly(urethane-urea), or a combination of one or more thereof. Which is selected from the group consisting of, method. 2. The method of claim 1, wherein the coordinating metal used to obtain the metal-tune functional olefin monomer is selected from the group consisting of aluminum, titanium, zinc, gallium, magnesium, calcium, and combinations of one or more thereof. in, how. 13. The method of claim 12, wherein the cyclic monomers used during the ring-opening polymerization (ROP) in step B) are selected from the group consisting of cyclic esters, macrolactones, cyclic carbonates, cyclic amides, cyclic urethanes and cyclic ureas; or combinations of one or more of these, a non-polar cyclic monomer having a ring size of at least 12 atoms. delete delete